WO2023190071A1 - Photosetting composition, three-dimensionally shaped article, mold, method for manufacturing cured product, and method for manufacturing plate denture - Google Patents

Photosetting composition, three-dimensionally shaped article, mold, method for manufacturing cured product, and method for manufacturing plate denture Download PDF

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Publication number
WO2023190071A1
WO2023190071A1 PCT/JP2023/011620 JP2023011620W WO2023190071A1 WO 2023190071 A1 WO2023190071 A1 WO 2023190071A1 JP 2023011620 W JP2023011620 W JP 2023011620W WO 2023190071 A1 WO2023190071 A1 WO 2023190071A1
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WIPO (PCT)
Prior art keywords
meth
acrylic monomer
group
photocurable composition
mold
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PCT/JP2023/011620
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French (fr)
Japanese (ja)
Inventor
卓 遠藤
俊一 酒巻
万依 木村
博紀 村井
孝曉 林
栄司 小林
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三井化学株式会社
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Publication of WO2023190071A1 publication Critical patent/WO2023190071A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/01—Palates or other bases or supports for the artificial teeth; Making same
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/20—Methods or devices for soldering, casting, moulding or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G

Definitions

  • the present disclosure relates to a method of manufacturing a photocurable composition, a three-dimensional molded object, a mold, a cured product, and a method of manufacturing a denture.
  • Patent Document 1 Patent No. 4160311
  • the conventional method utilizes room temperature polymerization using a mold, but this method can use many materials that can improve aesthetics and physical properties.
  • materials used in such room-temperature polymerization cannot often be used in stereolithography using a 3D printer. As a result, when stereolithography is performed using a 3D printer, it becomes difficult to make adjustments to obtain desired properties in the resulting denture.
  • the present inventors manufactured a mold for manufacturing a denture with a 3D printer using stereolithography, and discovered a method of manufacturing a denture with a denture using the mold.
  • the denture When removing a denture obtained by polymerizing a polymerizable composition in a mold from the mold, the denture may not fit into the mold due to the fact that the denture is equipped with artificial teeth. This may make it physically difficult to remove.
  • An object of one aspect of the present disclosure is to make it possible to create a mold in which the denture can be easily removed from the mold when manufacturing the denture using a mold or a mold that suppresses deformation during the manufacture of the denture.
  • An object of the present invention is to provide a photocurable composition, and a method for producing three-dimensional objects, molds, and cured products using this photocurable composition.
  • An object of another aspect of the present disclosure is to provide a method for manufacturing a denture that can be manufactured by a simple method.
  • the storage modulus of the test piece A1 at 25°C is 10 MPa or more
  • a photocurable composition in which the storage modulus of the test piece A1 at 37° C. is 400 MPa or less.
  • the (meth)acrylic monomer component is A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring, A di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and having no siloxane bond;
  • the photocurable composition according to ⁇ 1> comprising a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups.
  • a photocurable composition comprising a (meth)acrylic monomer component and a photopolymerization initiator,
  • the (meth)acrylic monomer component is A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring,
  • a di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and having no siloxane bond;
  • a photocurable composition comprising a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups.
  • ⁇ 4> The photocurable composition according to ⁇ 2> or ⁇ 3>, wherein the di(meth)acrylic monomer (Y) has a molecular weight of 400 to 5,000.
  • ⁇ 5> The photocurable composition according to any one of ⁇ 2> to ⁇ 4>, wherein the polyfunctional (meth)acrylic monomer (Z) has a molecular weight of 400 to 5,000.
  • ⁇ 6> Any one of ⁇ 2> to ⁇ 5>, wherein the content of the mono(meth)acrylic monomer (X) is 30% by mass to 90% by mass with respect to the total amount of the (meth)acrylic monomer component. 1.
  • ⁇ 7> Any one of ⁇ 2> to ⁇ 6>, wherein the content of the di(meth)acrylic monomer (Y) is 5% by mass to 55% by mass with respect to the total amount of the (meth)acrylic monomer component. 1.
  • the photocurable composition according to item 1. ⁇ 8> Any of ⁇ 2> to ⁇ 7>, wherein the content of the polyfunctional (meth)acrylic monomer (Z) is 1% by mass to 60% by mass with respect to the total amount of the (meth)acrylic monomer component.
  • the (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the Any one of ⁇ 1> to 11>, comprising a di(meth)acrylic monomer (A) having a distance of 25 ⁇ or more and 80 ⁇ or less between the oxygen atom forming the oxy group in the (meth)acryloyloxy group
  • the photocurable composition described in . ⁇ 13> The photocurable composition according to any one of ⁇ 1> to ⁇ 12>, which satisfies either of the following conditions (a) and (b).
  • the (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the other Two or more types of di(meth)acrylic monomers (A) having a distance of 25 ⁇ or more and 80 ⁇ or less from the oxygen atom forming the oxy group in the (meth)acryloyloxy group are included.
  • the (meth)acrylic monomer component is It has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group forms the oxy group in the other (meth)acryloyloxy group.
  • ⁇ 17> Any one of ⁇ 12> to ⁇ 16>, wherein the content of the di(meth)acrylic monomer (A) is 30% by mass or more based on the total amount of the (meth)acrylic monomer component.
  • ⁇ 18> The photocurable composition according to any one of ⁇ 1> to ⁇ 17>, which has a viscosity of 5 mPa ⁇ s to 6000 mPa ⁇ s as measured by an E-type viscometer at 25° C. and 50 rpm. thing.
  • ⁇ 19> The photocurable composition according to any one of ⁇ 1> to ⁇ 18>, which is a photocurable composition for stereolithography.
  • ⁇ 20> The photocurable composition according to any one of ⁇ 1> to ⁇ 19>, which is a photocurable composition used for manufacturing a mold by stereolithography.
  • ⁇ 21> A three-dimensional object comprising a cured product of the photocurable composition according to any one of ⁇ 1> to ⁇ 20>.
  • ⁇ 22> A mold including the three-dimensional structure according to ⁇ 21>.
  • ⁇ 23> The mold according to ⁇ 22>, which is used for manufacturing a denture.
  • a method for producing a cured product comprising a step of polymerizing the curable composition in the mold according to ⁇ 22> or ⁇ 23>.
  • a step of curing the photocurable composition by stereolithography to produce a mold used for manufacturing a denture A method for producing a denture with a denture, comprising the step of polymerizing a curable composition in the mold to produce a denture with a denture.
  • the present disclosure when producing a fixed denture using a mold or mold in which deformation during the production of a fixed denture is suppressed, it is possible to create a mold that allows easy removal of the fixed denture from within the mold.
  • the present invention provides a photocurable composition, a method for producing a three-dimensional object, a mold, a cured product, and a method for producing a denture using the photocurable composition.
  • a method for manufacturing a denture that can be manufactured by a simple method.
  • FIG. 2 is a schematic configuration diagram of a three-dimensional structure A2 formed in an example.
  • FIG. 3 is a schematic configuration diagram of a three-dimensional structure A3 formed in an example.
  • FIG. 3 is a schematic configuration diagram of a three-dimensional structure A4 formed in an example.
  • a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
  • the amount of each component contained in the composition is the total amount of the multiple substances present in the composition, unless otherwise specified. means quantity.
  • the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. .
  • the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
  • “light” is a concept that includes active energy rays such as ultraviolet rays and visible light.
  • (meth)acrylate means acrylate or methacrylate
  • (meth)acryloyl means acryloyl or methacryloyl
  • (meth)acrylic means acrylic or methacrylic
  • the photocurable compositions of the first embodiment and the second embodiment will be described.
  • the preferred embodiment of the first embodiment and the preferred embodiment of the second embodiment may be combined as appropriate.
  • Preferred uses and physical properties of the photocurable composition of the second embodiment are the same as those of the photocurable composition of the first embodiment, unless otherwise mentioned.
  • the photocurable composition of the first embodiment of the present disclosure is a photocurable composition containing a (meth)acrylic monomer component and a photopolymerization initiator, A cured layer A1 having a thickness of 50 ⁇ m is formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 , and by laminating the cured layer A1 in the thickness direction, the length A rectangular plate-shaped object A1 with a width of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet light with a wavelength of 365 nm at a dose of 3 J/cm 2 to form a long object.
  • the storage modulus of the test piece A1 at 25°C is 10 MPa or more
  • the storage modulus of the test piece A1 at 37° C. is 400 MPa or less.
  • the photocurable composition of the present disclosure includes a (meth)acrylic monomer component and a photopolymerization initiator, and the test piece A1 prepared under the above conditions has a storage modulus of 10 MPa or more at 25°C, and , the storage modulus of test piece A1 at 37° C. is 400 MPa or less.
  • the photocurable composition of the present disclosure is a composition that is cured by light irradiation, and a cured product can be obtained by curing this composition.
  • a preferred manufacturing method for manufacturing a cured product using the photocurable composition of the present disclosure is stereolithography.
  • the photocurable composition of the present disclosure is preferably a photocurable composition for stereolithography.
  • the cured product produced using the photocurable composition of the present disclosure is preferably a photocurable composition for stereolithography. (i.e., a cured product obtained by stereolithography).
  • Stereolithography is a method of stacking cured layers to obtain a cured product (i.e., a stereolithography) by repeating the operation of irradiating a photocurable composition with light to form a cured layer.
  • the stereolithography may be an inkjet stereolithography or a liquid bath stereolithography (that is, stereolithography using a liquid tank).
  • inkjet stereolithography droplets of a photocurable composition are ejected from an inkjet nozzle onto a substrate, and the droplets adhering to the substrate are irradiated with light to obtain a cured product.
  • a head including an inkjet nozzle and a light source is scanned in a plane, and a photocurable composition is discharged from the inkjet nozzle onto a base material, and the discharged photocurable composition is A cured layer is formed by irradiating the object with light, and these operations are repeated to sequentially stack the cured layers to obtain a cured product (that is, a stereolithographic object).
  • liquid bath method stereolithography a part of the photocurable composition (i.e., an uncured photocurable composition in a liquid state; the same applies hereinafter) contained in a liquid bath is cured by light irradiation. By forming layers and repeating this operation, cured layers are laminated to obtain a cured product (that is, a stereolithographic product).
  • Liquid bath type stereolithography differs from inkjet type stereolithography in that a liquid bath is used. Examples of liquid bath type stereolithography include DLP (Digital Light Processing) type stereolithography and SLA (Stereolithography) type stereolithography. In the DLP method, a planar light is irradiated onto the photocurable composition in a liquid tank.
  • the liquid bath type stereolithography is preferably DLP type stereolithography.
  • a vertically movable build table for example, A tray (i.e., a liquid tank) that is disposed below the build table (on the side in the gravity direction; the same applies hereinafter), includes a light-transmitting part, and contains a photocurable composition; a light source (e.g., an LED light source) disposed below the tray for irradiating the photocurable composition in the tray with planar light through the light-transmitting part of the tray; A 3D printer (for example, "Cara Print 4.0" manufactured by Kulzer, "Max UV” manufactured by Asiga, etc.) is used.
  • a light source e.g., an LED light source
  • a 3D printer for example, "Cara Print 4.0" manufactured by Kulzer, "Max UV” manufactured by Asiga, etc.
  • a one-layer gap is first created between the build table and the tray, and the gap is filled with a photocurable composition.
  • the photocurable composition filled in the gap is irradiated with planar light from below through the light-transmitting part of the tray, and the area irradiated with light is cured to form the first layer. form a hardened layer.
  • the gap between the build table and the tray is then widened by the next layer and the resulting space is filled with the photocurable composition.
  • the photocurable composition filling the space is irradiated with light in the same manner as for curing the first layer to form a second cured layer.
  • the manufactured three-dimensional structure may be further hardened by further irradiating the three-dimensional structure with light.
  • stereolithography using the DLP method for example, the descriptions in Japanese Patent No. 5111880 and Japanese Patent No. 5235056 may be referred to.
  • the use of the photocurable composition of the present disclosure is not particularly limited, and for example, it is preferably a photocurable composition used for manufacturing molds, dental products, etc. by stereolithography, and is suitable for manufacturing molds by stereolithography. It is more preferable that the photocurable composition is used.
  • the mold examples include molds used for manufacturing dentures. For example, with artificial teeth arranged in a mold, a curable composition for making a denture base is injected into the mold, and the curable composition after injection is cured to produce a denture with a denture.
  • dental products include dental prostheses, medical instruments used in the oral cavity, dental models, investment casting models, and the like.
  • dental prostheses include inlays, crowns, bridges, temporary crowns, and temporary bridges.
  • Medical devices used in the oral cavity include dentures (e.g., complete dentures, partial dentures, etc.), mouthpieces, mouth guards, orthodontic appliances, occlusal splints, and temporomandibular joints.
  • splints such as splints for medical treatment, trays for impression taking, surgical guides, etc.
  • the dental model include a tooth and jaw model.
  • the storage modulus of test piece A1 at 25° C. is 10 MPa or more, and from the viewpoint of suppressing mold deformation (for example, a mold made using the photocurable composition of the present disclosure).
  • the pressure is preferably 15 MPa or more, more preferably 30 MPa or more, and 50 MPa or more. It is even more preferable that there be.
  • the upper limit of the storage modulus of test piece A1 at 25°C is not particularly limited, and for example, from the viewpoint of ease of extraction from the mold (for example, to suppress damage to the mold, denture, etc. when pulling out the denture from the mold). viewpoint), the pressure may be 2000 MPa or less, 1000 MPa or less, or 500 MPa or less.
  • the storage modulus of test piece A1 at 37° C. is 400 MPa or less, and from the viewpoint of ease of extraction from the mold, it is preferably 300 MPa or less, and more preferably 250 MPa or less. It is preferably 200 MPa or less, and more preferably 200 MPa or less.
  • the lower limit of the storage modulus at 37°C of test piece A1 is not particularly limited, and for example, from the viewpoint of suppressing mold deformation during use, it may be 10 MPa or more, 30 MPa or more, 50 MPa or more. It may be.
  • the aromatic ring concentration in the (meth)acrylic monomer component is preferably from 0.0015 mol/g to 0.0042 mol/g, and preferably from 0.0016 mol/g to 0.0041 mol/g. It is more preferable that the amount is 0.0017 mol/g to 0.0040 mol/g.
  • the photocurable composition of the present disclosure satisfies any of the following conditions (1) to (3) from the viewpoint of being superior in extractability from a mold and suitably suppressing mold deformation during use. is preferred.
  • the aromatic ring concentration in the (meth)acrylic monomer component is 0.0030 mol/g to 0.0042 mol/g.
  • the aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol/g to 0.0035 mol/g, and the urethane bond concentration in the (meth)acrylic monomer component is 0.0001 mol/g to 0.0020 mol /g.
  • the aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol/g to 0.0035 mol/g, and the hydroxyl group concentration in the (meth)acrylic monomer component is 0.0005 mol/g to 0.0030 mol/g. It is g.
  • the urethane bond concentration in the (meth)acrylic monomer component may be 0.0001 mol/g to 0.0020 mol/g, or 0.0002 mol/g to 0.0018 mol/g, as described in (2) above. It may be 0.0004 mol/g to 0.0016 mol/g.
  • the hydroxyl group concentration in the (meth)acrylic monomer component may be 0.0005 mol/g to 0.0030 mol/g, or 0.0006 mol/g to 0.0025 mol/g, as described in (3) above. It may be 0.0008 mol/g to 0.0022 mol/g.
  • the photocurable composition of the present disclosure includes at least one (meth)acrylic monomer component.
  • the content of the (meth)acrylic monomer component relative to the total amount of the photocurable composition of the present disclosure is preferably 60% by mass or more, more preferably 80% by mass or more. It is preferably 90% by mass or more, and more preferably 90% by mass or more.
  • the upper limit of the content of the (meth)acrylic monomer component relative to the total amount of the photocurable composition of the present disclosure is not particularly limited, and may be less than 100% by mass, for example, may be 99.9% by mass or less. .
  • the (meth)acrylic monomer component means a monomer having one or more (meth)acryloyloxy groups in the molecule.
  • the photocurable composition of the present disclosure may or may not contain photopolymerizable components other than the (meth)acrylic monomer component.
  • photopolymerizable components other than the (meth)acrylic monomer component include styrene, styrene derivatives, (meth)acrylonitrile, and the like.
  • the content of photopolymerizable components other than the (meth)acrylic monomer component is 20% by mass or less based on the total amount of photopolymerizable components in the photocurable composition of the present disclosure. It may be 10% by mass or less, 5% by mass or less, or 1.0% by mass or less.
  • the lower limit of the content of photopolymerizable components other than the (meth)acrylic monomer component is not particularly limited, and may be, for example, 0% by mass or more.
  • the (meth)acrylic monomer constituting the (meth)acrylic monomer component is not particularly limited as long as it is a monomer having one or more (meth)acryloyloxy groups in the molecule.
  • a (meth)acrylic monomer may be a monofunctional (meth)acrylic monomer (i.e., a monomer having one (meth)acryloyloxy group in the molecule) or a difunctional (meth)acrylic monomer (i.e., a monomer having one (meth)acryloyloxy group in the molecule).
  • the monomer has two (meth)acryloyloxy groups
  • it is a polyfunctional (meth)acrylic monomer (i.e., a trifunctional or more functional (meth)acrylic monomer; i.e., a monomer with three or more (meth)acryloyl groups in the molecule.
  • a monomer having an oxy group may also be used.
  • the (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and one
  • the distance between an oxygen atom forming an oxy group in a (meth)acryloyloxy group and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group (hereinafter also referred to as distance d1) is , preferably contains a di(meth)acrylic monomer (A) having a thickness of 25 ⁇ or more and 80 ⁇ or less.
  • the (meth)acrylic monomer component may contain one type of di(meth)acrylic monomer (A) alone, or may contain two or more types of di(meth)acrylic monomer (A).
  • d1 i.e., the distance between the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the oxygen atom forming the oxy group in the other (meth)acryloyloxy group
  • d1 means the straight line distance between these two oxygen atoms.
  • d1 means a value determined using the "display distance measurement" function in "Chem 3D” (version 18.2.0.48) manufactured by PerkinElmer.
  • the d1 of the di(meth)acrylic monomer (A) is 25 ⁇ or more and 80 ⁇ or less, for example, may be 30 ⁇ or more and 60 ⁇ or less, or may be 30 ⁇ or more and 50 ⁇ or less.
  • the di(meth)acrylic monomer (A) contains a cyclic structure.
  • the cyclic structure include an aromatic structure and an alicyclic structure.
  • the di(meth)acrylic monomer (A) preferably contains an aromatic structure, and preferably contains a bisphenol structure such as bisphenol A and bisphenol F.
  • the di(meth)acrylic monomer (A) may have at least one of an ethyleneoxy group and a propyleneoxy group.
  • the molecular weight of the di(meth)acrylic monomer (A) is preferably 650 or more and 1,300 or less, more preferably 700 or more and 1,200 or less, and even more preferably 750 or more and 1,000 or less.
  • the weight average molecular weight of the di(meth)acrylic monomer (A) is preferably 650 or more and 1,300 or less, more preferably 700 or more and 1,200 or less, and even more preferably 750 or more and 1,000 or less. In this disclosure, weight average molecular weight is measured by gel permeation chromatography (GPC).
  • di(meth)acrylic monomer (A) ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, propoxylated bisphenol F di(meth)acrylate
  • examples include acrylate.
  • the content of the di(meth)acrylic monomer (A) is preferably 30% by mass or more, more preferably 40% to 100% by mass, and 50% by mass or more based on the total amount of the (meth)acrylic monomer component. More preferably, the amount is from % by mass to 100% by mass.
  • the (meth)acrylic monomer component should satisfy either of the following conditions (a) and (b) from the viewpoint of making it easier to form a mold that can easily ensure extractability and easily suppress deformation. preferable.
  • the (meth)acrylic monomer component contains two or more types of the aforementioned di(meth)acrylic monomers (A).
  • the (meth)acrylic monomer component is The aforementioned di(meth)acrylic monomer (A), A di(meth)acrylic monomer (B-1) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and a distance d1 of 10 ⁇ or more and less than 25 ⁇ , A di(meth)acrylic monomer (B-2) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and having a distance d1 of more than 80 ⁇ and less than 200 ⁇ , and one ( one or more (meth)acrylic monomers (B) selected from the group consisting of mono(meth)acrylic monomers (B-3) having a meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group; ,including.
  • the (meth)acrylic monomer component When the (meth)acrylic monomer component satisfies the above (a), the (meth)acrylic monomer component only needs to contain two or more types of di(meth)acrylic monomers (A), and other (meth)acrylic It may or may not contain a monomer component.
  • the (meth)acrylic monomer component By containing two or more types of di(meth)acrylic monomers (A), the (meth)acrylic monomer component not only lowers the storage modulus at 25°C and the storage modulus at 37°C of test piece A1, but also It is easier to control the reactivity than when one type of di(meth)acrylic monomer (A) is used, and the operability during stereolithography is excellent.
  • the total content of the di(meth)acrylic monomer (A) is 50% by mass to 100% by mass based on the total amount of the (meth)acrylic monomer component. It is preferably from 70% by mass to 100% by mass, even more preferably from 90% by mass to 100% by mass.
  • the (meth)acrylic monomer component contains the above-mentioned di(meth)acrylic monomer (A) and (meth)acrylic monomer (B).
  • the (meth)acrylic monomer component may each independently contain one type of di(meth)acrylic monomer (A) and (meth)acrylic monomer, or may contain two or more types thereof.
  • di(meth)acrylic monomer (B-1), di(meth)acrylic monomer (B-2) and mono(meth)acrylic monomer (B-3) classified as (meth)acrylic monomer (B) are I will explain the details.
  • the di(meth)acrylic monomer (B-1) has two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and the distance d1 is 10 ⁇ or more and less than 25 ⁇ (meth) It is an acrylic monomer component.
  • the use of di(meth)acrylic monomer (B-1) tends to increase the storage modulus at 25°C and the storage modulus at 37°C of test piece A1.
  • d1 of the di(meth)acrylic monomer (B-1) may be 12 ⁇ or more and 24 ⁇ or less, or 14 ⁇ or more and 22 ⁇ or less.
  • the molecular weight of the di(meth)acrylic monomer (B-1) is preferably 400 or more and 800 or less, more preferably 400 or more and 700 or less, and even more preferably 400 or more and 650 or less.
  • the weight average molecular weight of the di(meth)acrylic monomer (B-1) is preferably 400 or more and 800 or less, more preferably 400 or more and 700 or less, and even more preferably 400 or more and 650 or less.
  • the di(meth)acrylic monomer (B-1) has at least one of an aromatic ring and a urethane bond.
  • the di(meth)acrylic monomer (B-1) may contain only one of an aromatic ring and a urethane bond, or may contain both an aromatic ring and a urethane bond.
  • the di(meth)acrylic monomer (B-1) contains an aromatic ring and does not contain a urethane bond
  • the di(meth)acrylic monomer (B-1) has at least one of an ethyleneoxy group and a propyleneoxy group.
  • the di(meth)acrylic monomer (B-1) may have a bisphenol structure and at least one of an ethyleneoxy group and a propyleneoxy group.
  • di(meth)acrylic monomer (B-1) contains an aromatic ring and does not contain a urethane bond
  • specific examples of the di(meth)acrylic monomer (B-1) include ethoxylated bisphenol A di(meth)acrylate , propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, propoxylated bisphenol F di(meth)acrylate, and the like.
  • the di(meth)acrylic monomer (B-1) may contain a compound represented by the following formula (1).
  • R 1 is a divalent chain hydrocarbon group
  • R 2 and R 3 are each independently a divalent chain hydrocarbon group which may have a substituent
  • R 4 and R 5 are each independently a methyl group or a hydrogen atom.
  • the number of carbon atoms in the divalent chain hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 2 to 6.
  • the divalent chain hydrocarbon group in R 1 may be linear or branched, saturated or unsaturated, and may have a substituent.
  • the divalent chain hydrocarbon group in R 1 is preferably a straight chain or branched alkylene group having 1 to 20 carbon atoms, more preferably a straight chain or branched alkylene group having 1 to 12 carbon atoms, More preferably, it is a straight chain or branched alkylene group having 1 to 10 carbon atoms.
  • linear or branched alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, decanediyl group, undecanediyl group, dodecanediyl group, tridecanediyl group, tetradecanediyl group, pentadecanediyl group, octadecanediyl group, eicosylene group, vinylene group, propendiyl group, butenediyl group, pentendiyl group, ethynylene group, propynylene, A 2,4,4-trimethylhexylene group is mentioned.
  • R 2 and R 3 each independently represent a divalent chain hydrocarbon group which may have a substituent.
  • the divalent chain hydrocarbon groups suitable as R 2 and R 3 are the same as the divalent chain hydrocarbon groups suitable as R 1 .
  • the number of carbon atoms in the divalent chain hydrocarbon group which may have a substituent in R 2 and R 3 is preferably 2 to 6, more preferably 2 to 3.
  • R 2 and R 3 are divalent chain hydrocarbon groups having a substituent
  • substituents include; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; Aryl group; Cycloalkyl groups having 3 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group; tolyl group; xylyl group; Cumyl group; Styryl group; Alkoxyphenyl groups such as methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group; Examples include phenoxyalkyl groups such as phenoxymethyl group, phenoxyethyl group, and phenoxypropyl group.
  • ⁇ Di(meth)acrylic monomer (B-2) The di(meth)acrylic monomer (B-2) has two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and the distance d1 is more than 80 ⁇ and less than 200 ⁇ (meth) It is an acrylic monomer component.
  • the use of di(meth)acrylic monomer (B-2) tends to reduce the storage modulus at 25°C and the storage modulus at 37°C of test piece A1.
  • d1 of the di(meth)acrylic monomer (B-2) may be 85 ⁇ or more and 150 ⁇ or less, or 90 ⁇ or more and 120 ⁇ or less.
  • the molecular weight of the di(meth)acrylic monomer (B-2) is preferably 900 or more and 3000 or less, more preferably 1200 or more and 2500 or less, and even more preferably 1500 or more and 2000 or less.
  • the weight average molecular weight of the di(meth)acrylic monomer (B-2) is preferably 900 or more and 3000 or less, more preferably 1200 or more and 2500 or less, and even more preferably 1500 or more and 2000 or less.
  • the di(meth)acrylic monomer (B-2) has at least one of an aromatic ring and a urethane bond.
  • the di(meth)acrylic monomer (B-1) may contain only one of an aromatic ring and a urethane bond, or may contain both an aromatic ring and a urethane bond.
  • di(meth)acrylic monomer (B-2) contains a urethane bond, it may contain a compound represented by the following formula (2).
  • R 6 is each independently a divalent chain hydrocarbon group, a divalent hydrocarbon group having an aromatic structure, or a divalent hydrocarbon group having an alicyclic structure.
  • R 7 is each independently a divalent chain hydrocarbon group which may have a substituent
  • R 8 is a divalent linking group
  • R 9 and R 10 are each independently a methyl group or a hydrogen atom.
  • R 6 when R 6 is a divalent chain hydrocarbon group, the preferred configuration of R 6 is the same as the preferred configuration of R 1 in formula (1).
  • the divalent hydrocarbon group having an aromatic structure has 6 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, even more preferably 6 to 12 carbon atoms, and even more preferably 6 to 12 carbon atoms), which may have a substituent.
  • the divalent hydrocarbon group having an aromatic structure include an arylene group, an alkylenearylene group, an alkylenearylenealkylene group, and an arylenealkylenearylene group.
  • the divalent hydrocarbon group having an aromatic structure is preferably an alkylenearylene group or an alkylenearylenealkylene group.
  • arylene group examples include 1,3- or 1,4-phenylene group, 1,3- or 1,4-phenylene dimethylene group and 1,3- or 1,4-phenylene diethylene groups.
  • the divalent hydrocarbon group having an alicyclic structure preferably has 3 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and more preferably 6 to 8 carbon atoms. It is even more preferable.
  • Examples of the alicyclic structure include cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclohexenylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group, Cyclododecylene group, cyclotridecylene group, cyclotetradecylene group, cyclopentadecylene group, cyclooctadecylene group, cycloicosylene group, bicyclohexylene group, norbornylene group, isobornylene group, adamantylene group, methylenebiscyclo Examples include xylene group.
  • the divalent hydrocarbon group having an alicyclic structure in R 6 in formula (2) may have a substituent.
  • substituents include straight chain or branched alkyl groups having 1 to 6 carbon atoms.
  • R 7 is the same as the preferred configuration of R 2 and R 3 in formula (1).
  • R 8 is a divalent linking group.
  • the divalent linking group include a polyether group, an alkylene group, an arylene group, an alkylenearylene group, an alkylenearylenealkylene group, and the like. Among these, polyether groups are preferred, and polyether groups constituted by ether groups having 2 to 4 carbon atoms are more preferred.
  • the mono(meth)acrylic monomer (B-3) is a (meth)acrylic monomer component having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group.
  • the molecular weight of the mono(meth)acrylic monomer (B-3) is preferably 130 or more and 350 or less, more preferably 130 or more and 320 or less, and even more preferably 130 or more and 300 or less.
  • the weight average molecular weight of the mono(meth)acrylic monomer (B-3) is preferably 130 or more and 350 or less, more preferably 130 or more and 320 or less, and even more preferably 130 or more and 300 or less.
  • the mono(meth)acrylic monomer (B-3) may contain a compound represented by the following formula (3).
  • R 11 is a monovalent organic group having at least one of an aromatic structure and a hydroxy group.
  • the monovalent organic group having an aromatic structure in R 11 in formula (3) is preferably a monovalent organic group having 2 to 30 carbon atoms, and preferably a monovalent organic group having 3 to 20 carbon atoms. It is more preferable that there be.
  • R 11 may be an organic group represented by formula (4) below.
  • L 1 is a divalent chain hydrocarbon group which may have a single bond or a heteroatom which is O or N having 1 to 30 carbon atoms
  • A is a divalent chain hydrocarbon group having 2 to 30 carbon atoms. ⁇ 10 hydroxyalkyl group or an aryl group having 6 to 30 carbon atoms. * represents the bonding position.
  • the divalent chain hydrocarbon group represented by L 1 which may have a hetero atom of O or N having 1 to 30 carbon atoms may be linear or branched. It may be chain-like.
  • the carbon number of the divalent chain hydrocarbon group optionally having a hetero atom of O or N having 1 to 30 carbon atoms, represented by L 1 is more preferably 1 to 20, and 1 to 30 carbon atoms. It is more preferably from 1 to 10, and particularly preferably from 1 to 8.
  • the divalent chain hydrocarbon group represented by L 1 contains a heteroatom, the number of heteroatoms in L 1 is preferably 1 to 3, more preferably 1 or 2.
  • the divalent chain hydrocarbon group represented by L 1 may have a substituent. Suitable examples of the substituent include an alkyl group having 1 to 3 carbon atoms, a hydroxy group, and an alkyl group having 1 to 3 carbon atoms in which one or two of the hydrogen atoms are substituted with a hydroxy group.
  • the divalent chain hydrocarbon group represented by L 1 may include a urethane bond. When the divalent chain hydrocarbon group represented by L 1 contains a urethane bond, the number of urethane bonds in L 1 may be 1 or 2.
  • divalent chain hydrocarbon group represented by L 1 in formula (4) examples include the following groups.
  • * represents the bonding position.
  • L 1 is preferably a single bond.
  • the mono(meth)acrylic monomer (B-3) is preferably 4-hydroxybutyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.
  • the aromatic structure in the aryl group having 6 to 30 carbon atoms represented by A includes, for example, a phenyl structure, a biphenyl structure, a naphthyl structure, and an anthryl structure.
  • the group represented by A in formula (4) may have a substituent.
  • substituents include: an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; Hydroxy group; an alkyl group having 1 to 6 carbon atoms substituted with one or two hydroxy groups; Aryl group; Cycloalkyl groups having 3 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group; tolyl group; xylyl group; Cumyl group; Styryl group; Alkoxyphenyl groups such as methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group; Examples include phenoxyalkyl groups such as phenoxymethyl group, phenoxyethyl group, and phenoxypropyl group.
  • Examples of the group represented by A in formula (4) include the following examples. * represents the bonding position.
  • the content of the (meth)acrylic monomer (B) is preferably 3% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, based on the total amount of the (meth)acrylic monomer component.
  • the content is preferably 20% by mass to 60% by mass, more preferably 20% by mass to 60% by mass.
  • the total content of the di(meth)acrylic monomer (A) and the (meth)acrylic monomer (B) is 80% by mass or more based on the total amount of the (meth)acrylic monomer component contained in the photocurable composition of the present disclosure.
  • the content is preferably 90% by mass or more, and even more preferably 95% by mass or more.
  • the upper limit of the total content of di(meth)acrylic monomer (A) and (meth)acrylic monomer (B) is not particularly limited, and may be 100% by mass or less.
  • the photocurable composition of the present disclosure by increasing the content of acrylic groups among the methacrylic groups and acrylic groups of the (meth)acrylic monomer component (for example, increasing the content of the acrylic monomer in the photocurable composition). ), it is possible to improve the storage modulus of the test piece A1 at 25°C more preferentially than the storage modulus at 37°C.
  • the test The storage modulus of piece A1 at 37°C can be improved more preferentially than the storage modulus at 25°C.
  • the test The storage modulus at 25°C of piece A1 can be reduced more preferentially than the storage modulus at 37°C, and the content of methacrylic groups among the methacrylic groups and acrylic groups of the (meth)acrylic monomer component can be reduced.
  • the storage modulus of test piece A1 at 37°C is preferentially reduced over the storage modulus at 25°C. be able to.
  • the photocurable composition of the present disclosure includes a photopolymerization initiator.
  • the photocurable composition of the present disclosure may contain only one kind of photopolymerization initiator, or may contain two or more kinds of photopolymerization initiators.
  • the photopolymerization initiator is not particularly limited as long as it generates radicals when irradiated with light, and is preferably one that generates radicals at the wavelength of light used during stereolithography.
  • the wavelength of the light used during stereolithography is generally 365 nm to 500 nm, but is practically preferably 365 nm to 430 nm, and more preferably 365 nm to 420 nm.
  • photopolymerization initiators include acylphosphine oxide compounds, alkyl benzoylformates, alkylphenone compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, and thioxanthone compounds.
  • compounds, ⁇ -acyloxime ester compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, anthraquinone compounds, etc. can be mentioned.
  • acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. can be mentioned.
  • the total content of the photopolymerization initiator in the photocurable composition of the present disclosure is preferably 0.1% by mass to 5% by mass, and 0.5% by mass based on the total amount of the photocurable composition. It is more preferably 4% by mass, and even more preferably 0.5% by mass to 3% by mass.
  • the content of the acylphosphine oxide compound may be 50% by mass to 100% by mass, and 70% by mass based on the total amount of the photopolymerization initiator. % to 100% by mass, or 90% to 100% by mass.
  • the total content of two or more di(meth)acrylic monomers (A) and a photopolymerization initiator, or the total content of di(meth)acrylic monomers (A), (meth) ) is preferably 80% by mass or more, and preferably 90% by mass or more, each independently of the total amount of the photocurable composition of the present disclosure. It is more preferable that the amount is 95% by mass or more.
  • the upper limit of the total content of two or more types of di(meth)acrylic monomers (A) and photopolymerization initiator, or di(meth)acrylic monomer (A), (meth)acrylic monomer (B), and photopolymerization initiator is not particularly limited, and may be 100% by mass or less.
  • the photocurable composition of the present disclosure may contain one or more types of components other than the above-mentioned components, if necessary.
  • the total mass of the (meth)acrylic monomer component and the photopolymerization initiator is preferably 30% by mass or more based on the total amount of the photocurable composition, It is more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more.
  • ingredients include, for example, colorants, coupling agents such as silane coupling agents (for example, 3-acryloxypropyltrimethoxysilane), rubber agents, ion trapping agents, ion exchange agents, leveling agents, plasticizers, and erasers.
  • Additives such as foaming agents, thermal polymerization initiators, etc. may also be mentioned.
  • thermal polymerization initiator include thermal radical generators and amine compounds.
  • the photocurable composition of the present disclosure does not contain an inorganic filler (for example, silica, barium borosilicate glass, etc.; the same applies hereinafter), or When a filler is included, the content of the inorganic filler is 60% by mass or less (more preferably 40% by mass or less, still more preferably 20% by mass or less, particularly preferably 10% by mass or less) based on the total amount of the photocurable composition. It is preferable that
  • the method for preparing the photocurable composition of the present disclosure is not particularly limited.
  • Examples of the method for preparing the photocurable composition of the present disclosure include a method of mixing a (meth)acrylic monomer component, a photopolymerization initiator, and other components as necessary.
  • the means for mixing each component is not particularly limited, and includes means such as ultrasonic dissolution, a double-arm stirrer, a roll kneader, a twin-screw extruder, a ball mill kneader, and a planetary stirrer.
  • the photocurable composition of this embodiment may be prepared by mixing each component, filtering the mixture through a filter to remove impurities, and further performing a vacuum defoaming treatment.
  • the photocurable composition of the present disclosure preferably has a viscosity (hereinafter also simply referred to as "viscosity") measured by an E-type viscometer at 25° C. and 50 rpm of 5 mPa ⁇ s to 6000 mPa ⁇ s. .
  • rpm means revolutions per minute.
  • the viscosity is from 5 mPa ⁇ s to 6000 mPa ⁇ s, the photocurable composition has excellent handling properties when producing a cured product (particularly a stereolithographic product).
  • the viscosity is more preferably 10 mPa ⁇ s to 5000 mPa ⁇ s, even more preferably 20 mPa ⁇ s to 5000 mPa ⁇ s, even more preferably 100 mPa ⁇ s to 4500 mPa ⁇ s.
  • the photocurable composition of the second embodiment of the present disclosure is a photocurable composition containing a (meth)acrylic monomer component and a photopolymerization initiator, wherein the (meth)acrylic monomer component is A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring, at least one of a ring structure or a urethane bond, and two (meth)acryloyloxy groups, a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups; including.
  • the (meth)acrylic monomer component is A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring, at least one of a ring structure or a urethane bond, and two (meth)acryloyloxy groups, a polyfunctional (meth)acrylic monomer (Z) having a silox
  • the photocurable composition of the present disclosure includes a (meth)acrylic monomer component and a photopolymerization initiator, and the (meth)acrylic monomer component includes a mono(meth)acrylic monomer (X) and a di(meth)acrylic monomer (X). It includes an acrylic monomer (Y) and a polyfunctional (meth)acrylic monomer (Z).
  • a rectangular plate-shaped object A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 3 J/cm 2 by stereolithography.
  • the storage modulus of the test piece A1 at 25° C. is determined from the viewpoint of suppressing deformation of the mold (for example, applying a photocurable composition for making a denture base to a mold prepared using the photocurable composition of the present disclosure).
  • the pressure may be 10 MPa or more, and from the viewpoint of ease of extraction from the mold (for example, from the viewpoint of removing the denture from the mold, the mold when removing the denture from the mold, the denture, etc.) 100 MPa or less may be sufficient from the viewpoint of suppressing damage to
  • the storage modulus of the test piece A1 at 37° C. may be 400 MPa or less from the viewpoint of ease of extraction from the mold, and may be 6 MPa or more from the viewpoint of suppressing mold deformation during use.
  • the storage modulus of the test piece A1 at 25°C may be less than 10 MPa, for example, 1 MPa to 10 MPa, or 2 MPa to 8 MPa. Good too.
  • the storage modulus of the test piece A1 at 37° C. may be, for example, 0.5 MPa to 20 MPa, 1 MPa to 10 MPa, or 1 MPa to 6 MPa. It may be.
  • the releasability of a member manufactured using the mold (for example, a denture) from the mold is improved, and when the mold is released, The toughness of the cured product is improved and the cured product is less likely to break.
  • the (meth)acrylic monomer component includes a mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring.
  • a mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring.
  • the concentration of aromatic rings in the (meth)acrylic monomer component increases, which tends to make it easier to remove the denture from the mold (improving mold releasability). It tends to prevent breakage when the denture is taken out from inside (it has excellent toughness).
  • the mono(meth)acrylic monomer (X) is suitably used when adjusting the storage modulus at 25° C. and the storage modulus at 37° C. of the cured product of the photocurable composition to
  • the molecular weight of the mono(meth)acrylic monomer (X) may be from 160 to 400, or from 180 to 300.
  • the weight average molecular weight of the mono(meth)acrylic monomer (X) may be from 160 to 400, or from 180 to 300.
  • Two types of mono(meth)acrylic monomers (X) having different molecular weights may be used together. This tends to increase the dispersibility of the mono(meth)acrylic monomer (X) in the polymer and improve the shape recovery speed.
  • the mono(meth)acrylic monomer (X) is not particularly limited as long as it is a compound having one (meth)acryloyloxy group and an aromatic ring, and for example, a compound represented by the following formula (5). There may be.
  • R 1 is a divalent linking group
  • R 2 is an alkyl group or aryl group that may have a substituent
  • R 3 is a hydrogen atom or a methyl group
  • n is It is an integer from 0 to 5.
  • R 1 is an alkylene group, an arylene group (phenylene group, etc.), an alkylene arylene group (alkylene phenylene group, etc.), an arylene alkylene group (phenylene alkylene group, alkyleneoxy group, aryleneoxy group, or two thereof) A combination of the above may be used.Furthermore, the hydrogen atom contained in R1 may be substituted with a hydroxy group, an alkyl group, an aryl group, an amino group, or the like. In formula (5), the number of atoms in the main chain of R 1 may be from 1 to 20, or from 2 to 10. The number of carbon atoms in R 1 may be from 1 to 20, or from 2 to 10.
  • n is preferably 0 or 1.
  • R 2 is preferably a phenyl group which may have a substituent.
  • the number of carbon atoms in R 2 may be from 1 to 20, or from 1 to 10.
  • substituents that the alkyl group or aryl group in R 2 may have include a hydroxy group, an alkyl group, an aryl group, and an amino group.
  • the (meth)acrylic monomer component is a di(meth)acrylic monomer (Y) that has at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and does not have a siloxane bond.
  • the di(meth)acrylic monomer (Y) having a ring structure suitably contributes to suppressing deformation of a mold during the production of a denture and improving the water resistance of the mold. Further, when the ring structure includes an aromatic ring, the concentration of the aromatic ring in the (meth)acrylic monomer component tends to increase, the mold releasability increases, and the toughness tends to be excellent.
  • the di(meth)acrylic monomer (Y) having a urethane bond can suppress breakage when the denture is taken out from the mold, and tends to have excellent toughness. Further, the di(meth)acrylic monomer (Y) is suitably used when adjusting the storage modulus at 25° C. and the storage modulus at 37° C. of the cured product of the photocurable composition to be high.
  • the di(meth)acrylic monomer (Y) is not particularly limited as long as it is a compound that has at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and does not have a siloxane bond.
  • Examples of the ring structure include an aromatic ring structure and an alicyclic structure.
  • the di(meth)acrylic monomer (Y) has an oxygen atom forming an oxy group in one (meth)acryloyloxy group and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group.
  • the distance between them may be 10 ⁇ or more and 200 ⁇ or less.
  • the distance between the aforementioned oxygen atoms may be 10 ⁇ or more and less than 25 ⁇ , 25 ⁇ or more and 80 ⁇ or less, or more than 80 ⁇ and less than 200 ⁇ .
  • the elastic modulus of the mold can be increased and the deformation of the mold during the manufacture of dentures can be suppressed. This tends to improve mold releasability.
  • the molecular weight of the di(meth)acrylic monomer (Y) may be 400 to 5,000.
  • the weight average molecular weight of the di(meth)acrylic monomer (Y) may be from 400 to 4,000.
  • di(meth)acrylic monomers (Y) Two types of di(meth)acrylic monomers (Y) with different molecular weights may be used together. This tends to increase the dispersibility of the di(meth)acrylic monomer (Y) in the polymer and improve the shape recovery speed.
  • the di(meth)acrylic monomer (Y) may be a compound represented by the following formula (6-1) when it contains a urethane bond, and it may be a compound represented by the following formula (6-1) when it contains a ring structure. It may also be a compound represented by 2). When the di(meth)acrylic monomer (Y) contains both a urethane bond and a ring structure, it may be a compound represented by the following formula (6-1).
  • R 1 is an alkylene group, an ester bond, an alkyleneoxy group, or a combination of at least two of these, each of which may independently have a substituent
  • R 2 is a substituted an alkylene group which may have a group, a divalent ring structure, an ester bond, a urethane bond, an alkyleneoxy group, or a combination of at least two of these
  • R 3 is each independently a hydrogen atom or a methyl It is the basis.
  • R 3 is each independently a hydrogen atom or a methyl group
  • R 4 is each independently an optionally substituted alkylene group, alkyleneoxy group, or a combination thereof.
  • R 1 when R 1 is an alkylene group which may have a substituent or contains the alkylene group, examples of the substituent include a phenyloxy group.
  • the alkyleneoxy group may be an ethyleneoxy group, a propyleneoxy group, or the like.
  • the plurality of alkyleneoxy groups when a plurality of alkyleneoxy groups are included, the plurality of alkyleneoxy groups may be a polyethyleneoxy group, a polypropyleneoxy group, or the like.
  • R 1 when R 1 has an ester bond, R 1 may contain a structural unit derived from ⁇ -caprolactone, or may contain a plurality of structural units derived from ⁇ -caprolactone.
  • R 1 when R 1 has an ester bond, it may be an alkylene group -O-CO-alkylene group, and among these, the -O-CO-alkylene group may have a repeating structure (for example, 2 to 10). .
  • the number of carbon atoms in R 1 may be from 1 to 50, or from 2 to 25.
  • R 2 when R 2 is an alkylene group (which may be linear or branched) that may have a substituent, examples of the substituent include a hydroxy group, an alkyl group, aryl group, amino group, etc.
  • R 2 when R 2 is a divalent ring structure or includes a divalent ring structure, examples of the ring structure include an aromatic ring or an alicyclic ring, and specifically, a phenylene group. , cyclohexylene group. Furthermore, R 2 may include a group formed by a divalent ring structure and a divalent alkylene group (eg, an isophorone group, a methylenebis(cyclohexylene) group). In addition, R 2 is a divalent hydrocarbon group containing two ring structures, two urethane bonds, and a divalent linking group containing an alkyleneoxy group (for example, a divalent hydrocarbon group containing a ring structure - a urethane bond). - (poly)alkyleneoxy group - urethane bond - divalent hydrocarbon group containing a ring structure). The number of carbon atoms in R 2 may be from 1 to 200, or from 2 to 100.
  • R 4 is an alkyleneoxy group
  • R 5 may be an oxygen atom
  • R 4 is an alkylene group
  • R 6 may be a phenylene group or a bisphenol skeleton (eg, a bisphenol A skeleton or a bisphenol F skeleton).
  • the number of carbon atoms in R 4 may be from 1 to 50, or from 2 to 30.
  • the number of carbon atoms in R 6 may be from 1 to 50, or from 2 to 20.
  • the (meth)acrylic monomer component includes a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups.
  • a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups.
  • the aromatic ring concentration in the (meth)acrylic monomer component increases, which tends to make it easier to remove the denture from the mold (improving mold releasability), It has excellent deformability when manufacturing dentures, and tends to have excellent dimensional accuracy.
  • the polyfunctional (meth)acrylic monomer (Z) is suitably used when adjusting the storage modulus at 25° C. and the storage modulus at 37° C. of the cured product of the photocurable composition to be low.
  • the polyfunctional (meth)acrylic monomer (Z) has a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups.
  • the polyfunctional (meth)acrylic monomer (Z) may contain a plurality of siloxane bonds (Si-O-Si), and more specifically, a linear siloxane bond, a ladder-like siloxane containing a linear chain and a branch. It may contain bonds, cage-type siloxane bonds, and the like.
  • the polyfunctional (meth)acrylic monomer (Z) may contain two or more (meth)acryloyloxy groups.
  • siloxane bond examples include a dimethylsiloxane bond, a methylphenylsiloxane bond, a diphenylsiloxane bond, and the like, with a dimethylsiloxane bond being preferred.
  • the polyfunctional (meth)acrylic monomer (Z) may be a compound containing a siloxane bond (Si-O-Si) and three or more (meth)acryloyloxy groups, and three or more (meth)acryloyloxy groups. It may also be a silsesquioxane containing an acryloyloxy group.
  • the polyfunctional (meth)acrylic monomer (Z) may have a molecular weight of 400 to 5,000.
  • the weight average molecular weight of the polyfunctional (meth)acrylic monomer (Z) may be from 400 to 4,000.
  • the polyfunctional (meth)acrylic monomer (Z) may be a compound represented by the following formula (7).
  • R 1 is an alkylene group that may each independently have a substituent
  • R 2 is an alkylene group that may each independently have a substituent
  • R 3 are each independently a hydrogen atom or a methyl group
  • R4 is each independently an alkyl group, a hydrogen atom, or an aryl group
  • m is an integer of 0 or more
  • n is an integer of 0 or more
  • l is an integer greater than or equal to 0.
  • R 1 is preferably a methylene group, ethylene group or propylene group
  • R 2 is more preferably a methylene group, ethylene group, propylene group or butylene group.
  • R 4 is preferably a methyl group or a phenyl group, more preferably a methyl group.
  • m may be from 1 to 30, or from 2 to 20. From the viewpoint of compatibility with other (meth)acrylic monomer components, m is preferably 30 or less, more preferably 20 or less.
  • n may be 0 or 1 or more. When n is 1 or more, n may be from 1 to 30, or from 1 to 20.
  • l may be 0 or 1 or more. When l is 1 or more, l may be from 1 to 30, or from 1 to 20.
  • the content of the mono(meth)acrylic monomer (X) is preferably from 30% by mass to 90% by mass, and from 40% by mass to the total amount of the (meth)acrylic monomer component. More preferably, it is 80% by mass.
  • the content of the di(meth)acrylic monomer (Y) is preferably from 5% by mass to 55% by mass, and from 10% by mass to the total amount of the (meth)acrylic monomer component. More preferably, it is 40% by mass.
  • the content of the polyfunctional (meth)acrylic monomer (Z) is preferably 1% by mass to 60% by mass, and 5% by mass based on the total amount of the (meth)acrylic monomer component. % to 50% by mass is more preferable.
  • the total content of mono(meth)acrylic monomer (X), di(meth)acrylic monomer (Y), and polyfunctional (meth)acrylic monomer (Z) is 50% by mass to 100% by mass. %, more preferably 70% to 100% by weight, even more preferably 90% to 100% by weight.
  • the siloxane bond concentration in the composition is preferably 0.100 mmol/g to 3.000 mmol/g, more preferably 0.300 mmol/g to 2.500 mmol/g.
  • the siloxane bond concentration is 0.100 mmol/g or more, mold release properties tend to improve, and when it is 3.000 mmol/g or less, it is possible to suppress breakage when taking out the denture from the mold, and improve toughness. They tend to be excellent at
  • the aromatic ring concentration in the (meth)acrylic monomer component is preferably 0.0015 mol/g to 0.0070 mol/g, more preferably 0.0020 mol/g to 0.0065 mol/g.
  • the siloxane bond concentration in the composition and the aromatic ring concentration in the (meth)acrylic monomer component each satisfy the aforementioned numerical ranges.
  • the total content of the mono(meth)acrylic monomer (X), the di(meth)acrylic monomer (Y), the polyfunctional (meth)acrylic monomer (Z), and the photopolymerization initiator is the same as that of the photocurable composition of the present disclosure. It is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total amount.
  • the upper limit of the total content of mono(meth)acrylic monomer (X), di(meth)acrylic monomer (Y), polyfunctional (meth)acrylic monomer (Z), and photopolymerization initiator is not particularly limited, and is 100% by mass. The following is sufficient.
  • the three-dimensional structure of the present disclosure includes a cured product of the photocurable composition of the present disclosure. Therefore, when the three-dimensional molded object of the present disclosure is a mold, deformation during the production of the denture can be suppressed, and when the denture is manufactured using the mold, the denture is removed from the mold. It becomes easier. It is preferable that the three-dimensional shaped article of the present disclosure includes a cured product obtained by stereolithography (i.e., a stereolithographic article). The method for producing a cured product (for example, a stereolithographic product) is as described above.
  • a preferred embodiment of the three-dimensional structure includes a mold, and more specifically, a mold used for manufacturing a denture.
  • the method for producing a cured product of the present disclosure includes the step of polymerizing the curable composition in the mold described above.
  • a mold is produced using the photocurable composition of the present disclosure described above, the curable composition is injected into the produced mold, and the injected curable composition is polymerized to produce a cured product. do it.
  • the curable composition injected into the mold is not particularly limited as long as it contains a polymerizable component that is polymerized by heat, light, or the like.
  • a conventionally known curable composition for making a denture base is injected into the mold, and the curable composition for making a denture base after injection is injected into the mold. may be cured.
  • the method for manufacturing a denture with a denture of the present disclosure includes a step of curing a photocurable composition by stereolithography to produce a mold used for manufacturing the denture with a denture, polymerizing the curable composition in the mold, A step of manufacturing a fixed denture.
  • the method for manufacturing a denture with a backing according to the present disclosure is a method of manufacturing a denture with a backing through two steps: a step of making a mold and a step of manufacturing a denture with a backing, and a method of manufacturing a denture with a backing using a conventional mold.
  • a denture with a backing can be manufactured using a method that is simpler than a method for manufacturing a denture.
  • the process of producing a mold includes, for example, a process of acquiring three-dimensional impression data in the oral cavity of a denture user, a process of acquiring mold data from the acquired three-dimensional impression data, and a process of acquiring mold data. It is preferable to include a step of curing the photocurable composition by stereolithography based on.
  • the process of manufacturing dentures includes the steps of arranging artificial teeth in a mold, injecting a curable composition for making a denture base into the mold with the artificial teeth arranged in the mold, and post-injection steps. It is preferable to include the steps of curing the curable composition and removing the manufactured denture from the mold.
  • the photocurable composition used to create the mold is not particularly limited.
  • the photocurable composition of the present disclosure is preferable to use as a photocurable composition used for producing a mold.
  • a rectangular plate-shaped object A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 3 J/cm 2 by stereolithography.
  • a rectangular plate-shaped test piece A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was prepared.
  • the produced test piece A1 was measured by dynamic viscoelasticity measurement under the conditions of a measurement frequency of 1 Hz while increasing the temperature in a temperature range of 25°C to 200°C and a heating rate of 3°C/min.
  • the storage modulus and the storage modulus at 37°C were determined.
  • the test piece A1 was prepared using a DLP 3D printer (Kulzer, Cara Print 4.0), and the storage modulus was measured using a dynamic viscoelasticity measurement device (DMA7100, Hitachi High-Tech Science Co., Ltd.). This was done using
  • viscosity The viscosity of the obtained photocurable composition was measured using an E-type viscometer at 25° C. and 50 rpm. As a result, the viscosities of the photocurable compositions of Examples 1 to 19 were all in the range of 50 mPa ⁇ s to 3000 mPa ⁇ s.
  • test piece A2 has L of 28 mm, L' of 20 mm, W of 2 mm, H of 24 mm, H' of 22 mm, and width (D) of 2 mm.
  • the shape has a gap of .
  • a deviation from the design value was evaluated as "A”
  • B a deviation of 0.05 mm or more and 0.10 mm or less
  • C a deviation larger than 0.10 mm
  • test piece A3 has L of 15 mm, L' of 2 mm, H of 12 mm, H' of 2 mm, R of 4 mm, and thickness (D) of 10 mm. It has the shape of An attachment/detachment test was conducted by inserting and removing an iron ball (diameter 10 mm) between the two semicircular columns of the obtained test piece A3 at a moving speed of 120.0 ⁇ 2.0 mm/min. Observe the test piece after moving it in and out 10 times, and evaluate it as "A” if there is no shape change and no cracking after the test, "B” if there is shape change and no cracking after the test, and "C” if cracking occurs after the test. did.
  • Photopolymerizable component 1 Ethoxylated bisphenol A diacrylate (A-BPE-10, Shin Nakamura Chemical Co., Ltd.)
  • Photopolymerizable component 2 Ethoxylated bisphenol A dimethacrylate (BPE-500, manufactured by Shin Nakamura Chemical Co., Ltd.)
  • Photopolymerizable components 3 to 9 are di(meth)acrylic monomers (meth)acrylic monomers having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and a distance d1 of 10 ⁇ or more and less than 25 ⁇ . Classified as B-1).
  • the photopolymerizable component 10 is a di(meth)acrylic monomer (B- It is classified as 2).
  • Photopolymerizable components 11 to 17 are classified as mono(meth)acrylic monomers (B-3) having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group.
  • Photopolymerizable component 3 Ethoxylated bisphenol A diacrylate (BP-4EAL, Kyoeisha Chemical Co., Ltd.)
  • Photopolymerizable component 4 Ethoxylated bisphenol A dimethacrylate (SR540, Sartomer Co., Ltd.)
  • Photopolymerizable component 5 Ethoxylated bisphenol F diacrylate (M-208, Toagosei Co., Ltd.)
  • Photopolymerizable component 6 Ethoxylated bisphenol A dimethacrylate (SR348, Sartomer Co., Ltd.)
  • Photopolymerizable component 7 Urethane diacrylate (SUA-1 (UDA in the table), compound produced according to Production Example 1A below)
  • Photopolymerizable component 8 Urethane dimethacrylate (SUA-2 (UDMA in the table), compound produced according to Production Example 1B below)
  • Photopolymerizable component 9 Bifunctional urethane acrylate (AH-600, Kyoeisha
  • Photopolymerizable component 18 Ethoxylated hydrogenated bisphenol A dimethacrylate (HBPEM-10, Daiichi Kogyo Seiyaku Co., Ltd.)
  • Photopolymerizable component 19 Ethoxylated hydrogenated bisphenol A diacrylate (HBPE-4, Daiichi Kogyo Seiyaku Co., Ltd.)
  • Photoinitiator 1 Acylphosphine oxide compound (Omnirad 819: “Omnirad 819” manufactured by IGM Resins B.V.)
  • Photoinitiator 2 Acylphosphine oxide compound (Omnirad TPO: “Omnirad TPO” manufactured by IGM Resins B.V.)
  • TMHDI trimethylhexamethylene diisocyanate
  • reaction temperature was maintained at 80°C and the reaction was carried out for 5 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction.
  • HPLC analysis By discharging the product from the reactor, 840 g of urethane acrylate (SUA-3) was obtained.
  • the viscosity at 40°C was 41000 mPa ⁇ s.
  • Example 20 ⁇ Manufacture of dentures> A plaster model of the upper or lower jaw was used as three-dimensional impression data using a laboratory dental scanner (Kulzer, Cara Scan 4.0). Each three-dimensional impression data was uploaded to commercially available CAD software (3D Systems, Geomagic Design X). A mold for manufacturing dentures was designed on CAD software, the thickness of the mold was set to 2.0 mm, and three-dimensional modeling data was obtained.
  • CAD software 3D Systems, Geomagic Design X
  • the photocurable composition of Example 1 was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer with a thickness of 50 ⁇ m, and the cured layers were laminated in the thickness direction, and the above
  • a molded article for manufacturing dentures with a base was obtained.
  • the resulting molded article was irradiated with ultraviolet rays with a wavelength of 365 nm under conditions of 3 J/cm 2 to fully cure the article, thereby obtaining a mold for manufacturing dentures.
  • this method allows for the creation of dentures more easily than conventional wax dentures, manual methods using silicone, etc., and the use of denture resin, which is unsuitable for stereolithography, for the production of dentures. Therefore, it is suitable for obtaining desired physical properties.
  • L is 24 mm
  • L' is 20 mm
  • W is 2 mm
  • H is 5 mm
  • H' is 3 mm
  • D is 14 mm. It has a shape in which D' is 10 mm.
  • test piece A4 is peeled off from the denture manufacturing polymer.
  • the surface of the polymer for making dentures that was in contact with test piece A4 was observed using a 3D shape measuring machine (Keyence Corporation, VR-3200), and the surface that was in contact with the polymer for making dentures after being removed was observed.
  • the area value of test piece A4 was calculated, and the adhesion rate to the surface (200 mm 2 ) consisting of L' and D' was calculated. The smaller the adhesion rate, the better the mold releasability.
  • the evaluation was made as "A" when there was no surface adhesion, "B” when surface adhesion was less than 5%, and "C” when surface adhesion was 5% or more.
  • the obtained photocurable composition was printed using a 3D printer (Kulzer, Cara Print 4.0) to a size of 8 mm long x 39 mm wide under the conditions of a visible light wavelength of 405 nm and a visible light illuminance of 8.0 mJ/ cm2.
  • a molded article (layer width 50 ⁇ m) was obtained by molding to a thickness of 4 mm.
  • An optically shaped article was obtained by irradiating the obtained article with ultraviolet rays with a wavelength of 365 nm under conditions of 10 J/cm 2 to fully cure the article.
  • test piece stress was applied to curve the test piece so that both ends of the test piece in the longitudinal direction (horizontal direction) were in contact with each other, and the test piece was held for 10 seconds. Thereafter, the stress was released and changes in the shape of the test piece were observed and evaluated based on the following criteria. A: It returned to its original shape within 1 second after stress was released. B: It took more than 1 second to return to its original shape after stress was released.
  • ⁇ Mono(meth)acrylic monomer (X)> The structure of each mono(meth)acrylic monomer (X) listed in Tables 4 to 7 is as follows.
  • PO-A manufactured by Kyoeisha Chemical Co., Ltd. PO manufactured by Kyoeisha Chemical Co., Ltd.
  • ⁇ Di(meth)acrylic monomer (Y)> The structure of each di(meth)acrylic monomer (Y) listed in Tables 4 to 7 is as follows.
  • SUA-1 Compound produced by the method described in Production Example 1A below (UDA in the table) ABE-300 A-BPE-10 manufactured by Shin Nakamura Chemical Co., Ltd. SA-001 manufactured by Shin Nakamura Chemical Co., Ltd.
  • Compound produced by the method described in Production Example 1C below U1 in the table
  • reaction product was dissolved in 500 g of toluene, neutralized with 10% NaOH aqueous solution, and then washed with 150 g of 5% ammonium sulfate aqueous solution. Toluene was distilled under reduced pressure to obtain 390 g of di(meth)acrylic monomer (SA-001). The viscosity at 25°C was 410 mPa ⁇ s.
  • reaction temperature was maintained at 70°C and the reaction was carried out for 5 hours. Thereafter, the reaction solution was neutralized with a 10% NaOH aqueous solution, and then washed with 150 g of a 5% ammonium sulfate aqueous solution. Ethyl acetate was distilled under reduced pressure to obtain 440 g of polyfunctional (meth)acrylic monomer (SiA-001). The viscosity at 25°C was 110 mPa ⁇ s.
  • Photopolymerization initiator As the photopolymerization initiator listed in Tables 4 to 7, the aforementioned photopolymerization initiator 1 (acylphosphine oxide compound, Omnirad 819: “Omnirad 819" manufactured by IGM Resins B.V.) was used.

Abstract

This photosetting composition comprises a (meth)acrylic monomer component and a photoinitiator. When a cured layer A1 having a thickness of 50 µm is obtained by irradiating the photosetting composition with visible light having a wavelength of 405 nm at an irradiation quantity of 11 mJ/cm2, a rectangular plate-like shaped article A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is obtained by layering the cured layer A1 in the thickness direction, and a rectangular plate-like test piece A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is prepared through optical shaping by irradiating the shaped article A1 with ultraviolet rays having a wavelength of 365 nm at an irradiation quantity of 3 J/cm2, the storage modulus of the test piece A1 at 25°C is 10 MPa or more and the storage modulus of the test piece A1 at 37°C is 400 MPa or less.

Description

光硬化性組成物、立体造形物、鋳型、硬化物を製造する方法及び有床義歯の製造方法Method for producing a photocurable composition, three-dimensional model, mold, cured product, and method for producing a denture
　本開示は、光硬化性組成物、立体造形物、鋳型、硬化物を製造する方法及び有床義歯の製造方法に関する。 The present disclosure relates to a method of manufacturing a photocurable composition, a three-dimensional molded object, a mold, a cured product, and a method of manufacturing a denture.
　近年、歯科用補綴物、口腔内で使用される器具などの歯科用製品に関する検討がなされている。例えば、これら歯科用製品の造形の効率の観点で、３Ｄプリンタを用いた光造形により歯科用製品等の立体造形物を製造する方法が知られている（例えば、特許文献１参照）。
　　［特許文献１］特許４１６０３１１号公報 In recent years, studies have been made regarding dental products such as dental prostheses and instruments used in the oral cavity. For example, from the viewpoint of the efficiency of modeling these dental products, a method of manufacturing three-dimensional objects such as dental products by stereolithography using a 3D printer is known (see, for example, Patent Document 1).
[Patent Document 1] Patent No. 4160311
　一方、３Ｄプリンタなどの光造形を使用せずに、歯科用補綴物、有床義歯等を作製する方法が従来から存在する。
　その方法によると、例えば、有床義歯を製造する場合、まず、患者から直接口腔内の型を印象材を使用して取得し、その印象材を参照して患者の口腔内を模した模型を作製する。その模型からシリコーンで型取りする。その型取りされたものを鋳型として、これに、硬化性組成物を注入し、常温重合により有床義歯を製造することができる。
　この光造形を用いない従来法によると、上記のとおり、患者の口腔内を模した模型を作製したり、シリコーンで型取りしたりするなどの工程が煩雑であるという課題がある。 On the other hand, there have conventionally been methods for producing dental prostheses, dentures, etc. without using stereolithography such as a 3D printer.
According to this method, for example, when manufacturing dentures, first, a mold of the patient's oral cavity is obtained directly from the patient using an impression material, and a model of the patient's oral cavity is created by referring to the impression material. Create. A silicone mold is made from the model. Using the molded product as a mold, a curable composition is injected into the mold and polymerized at room temperature to produce a denture.
As mentioned above, this conventional method that does not use stereolithography has a problem in that the steps such as creating a model of the patient's oral cavity and making a silicone mold are complicated.
これに対し、３Ｄプリンタを用いた光造形により有床義歯を直接製造する方法によれば、上記煩雑さは解消される。しかしながら、３Ｄプリンタを用いない従来法と比較すると、光造形により適切に硬化できる材料が非常に限定的であることから、得られる有床義歯の特長も限定的なものになってしまう。例えば、従来法では、鋳型を用いて常温重合を利用するものであるが、この方法では、審美性を向上させたり、物性を向上させたりすることが可能な材料が多く利用できる。これに対し、このような常温重合で使用される材料は３Ｄプリンタによる光造形では使用できないことが多い。結果的に、３Ｄプリンタを用いた光造形によると、得られる有床義歯において所望の性質を得るための調整が難しくなってしまう。 On the other hand, according to a method of directly manufacturing a denture with a denture by stereolithography using a 3D printer, the above-mentioned complexity is eliminated. However, compared to the conventional method that does not use a 3D printer, the materials that can be appropriately cured by stereolithography are very limited, so the features of the resulting denture are also limited. For example, the conventional method utilizes room temperature polymerization using a mold, but this method can use many materials that can improve aesthetics and physical properties. On the other hand, materials used in such room-temperature polymerization cannot often be used in stereolithography using a 3D printer. As a result, when stereolithography is performed using a 3D printer, it becomes difficult to make adjustments to obtain desired properties in the resulting denture.
　以上のとおり、簡潔に有床義歯を作製でき、かつ、所望の性質を得るための調整がしやすい有床義歯の製造方法が求められている。 As described above, there is a need for a method for manufacturing dentures that can be easily manufactured and that can be easily adjusted to obtain desired properties.
　上記目的を達成するために、本発明者らは、有床義歯製造用の鋳型を３Ｄプリンタによる光造形で製造し、その鋳型を用いて有床義歯を製造する方法を見出した。 In order to achieve the above object, the present inventors manufactured a mold for manufacturing a denture with a 3D printer using stereolithography, and discovered a method of manufacturing a denture with a denture using the mold.
　一方、このように、光硬化性組成物により有床義歯の鋳型を作製し、その鋳型を用いて有床義歯を製造する場合、有床義歯の製造に用いる重合性組成物の種類によっては、有床義歯の製造時における鋳型に流し込んだ重合性組成物が重合する際に鋳型そのものが収縮して変形してしまうことがある。そうすると、結果的に得られる有床義歯も変形してしまう場合がある。 On the other hand, when creating a mold for a denture using a photocurable composition and manufacturing the denture using the mold, depending on the type of polymerizable composition used for manufacturing the denture, When a polymerizable composition poured into a mold during the manufacture of dentures polymerizes, the mold itself may shrink and become deformed. In this case, the resulting denture may also be deformed.
　鋳型内で重合性組成物を重合させて得られた有床義歯を鋳型内から取り出す際に、有床義歯が人工歯を備えていることなどに起因して有床義歯が鋳型内に嵌まってしまい、物理的に取り出しにくくなる場合がある。 When removing a denture obtained by polymerizing a polymerizable composition in a mold from the mold, the denture may not fit into the mold due to the fact that the denture is equipped with artificial teeth. This may make it physically difficult to remove.
　本開示の一態様の目的は、有床義歯の製造時における変形が抑制された鋳型又は鋳型を用いて有床義歯を製造する際に、鋳型内から有床義歯を取り出しやすい鋳型の作製が可能な光硬化性組成物、並びにこの光硬化性組成物を用いた立体造形物、鋳型及び硬化物を製造する方法を提供することである。
　本開示の他の一態様の目的は、簡便な方法で有床義歯を作製可能である有床義歯の製造方法を提供することである。 An object of one aspect of the present disclosure is to make it possible to create a mold in which the denture can be easily removed from the mold when manufacturing the denture using a mold or a mold that suppresses deformation during the manufacture of the denture. An object of the present invention is to provide a photocurable composition, and a method for producing three-dimensional objects, molds, and cured products using this photocurable composition.
An object of another aspect of the present disclosure is to provide a method for manufacturing a denture that can be manufactured by a simple method.
　上記課題を解決する手段には、以下の態様が含まれる。
＜１＞　（メタ）アクリルモノマー成分と、光重合開始剤と、を含む光硬化性組成物であって、
　前記光硬化性組成物に対し波長４０５ｎｍの可視光を照射量１１ｍＪ／ｃｍ２にて照射して厚み５０μｍの硬化層Ａ１を形成し、前記硬化層Ａ１を厚み方向に積層させることにより、長さ４０ｍｍ、幅１０ｍｍ、厚み１．０ｍｍの矩形板形状の造形物Ａ１を形成し、前記造形物Ａ１に対し、波長３６５ｎｍの紫外線を照射量３Ｊ／ｃｍ２にて照射する条件の光造形により、長さ４０ｍｍ、幅１０ｍｍ、厚み１．０ｍｍの矩形板形状の試験片Ａ１を作製した場合に、
　前記試験片Ａ１の２５℃における貯蔵弾性率が１０ＭＰａ以上であり、
　前記試験片Ａ１の３７℃における貯蔵弾性率が４００ＭＰａ以下である、光硬化性組成物。
＜２＞　前記（メタ）アクリルモノマー成分が、
　１つの（メタ）アクリロイルオキシ基と、芳香環と、を有するモノ（メタ）アクリルモノマー（Ｘ）と、
　環構造又はウレタン結合の少なくともいずれか一方と、２つの（メタ）アクリロイルオキシ基と、を有し、シロキサン結合を有さないジ（メタ）アクリルモノマー（Ｙ）と、
　シロキサン結合と、２つ以上の（メタ）アクリロイルオキシ基と、を有する多官能（メタ）アクリルモノマー（Ｚ）と、を含む、＜１＞に記載の光硬化性組成物。
＜３＞　（メタ）アクリルモノマー成分と、光重合開始剤と、を含む光硬化性組成物であって、
　前記（メタ）アクリルモノマー成分が、
　１つの（メタ）アクリロイルオキシ基と、芳香環と、を有するモノ（メタ）アクリルモノマー（Ｘ）と、
　環構造又はウレタン結合の少なくともいずれか一方と、２つの（メタ）アクリロイルオキシ基と、を有し、シロキサン結合を有さないジ（メタ）アクリルモノマー（Ｙ）と、
　シロキサン結合と、２つ以上の（メタ）アクリロイルオキシ基と、を有する多官能（メタ）アクリルモノマー（Ｚ）と、を含む、光硬化性組成物。
＜４＞　前記ジ（メタ）アクリルモノマー（Ｙ）の分子量が、４００～５０００である、＜２＞又は＜３＞に記載の光硬化性組成物。
＜５＞　前記多官能（メタ）アクリルモノマー（Ｚ）の分子量が、４００～５０００である、＜２＞～＜４＞のいずれか１つに記載の光硬化性組成物。
＜６＞　前記モノ（メタ）アクリルモノマー（Ｘ）の含有量が、前記（メタ）アクリルモノマー成分の全量に対し、３０質量％～９０質量％である、＜２＞～＜５＞のいずれか１つに記載の光硬化性組成物。
＜７＞　前記ジ（メタ）アクリルモノマー（Ｙ）の含有量が、前記（メタ）アクリルモノマー成分の全量に対し、５質量％～５５質量％である、＜２＞～＜６＞のいずれか１つに記載の光硬化性組成物。
＜８＞　前記多官能（メタ）アクリルモノマー（Ｚ）の含有量が、前記（メタ）アクリルモノマー成分の全量に対し、１質量％～６０質量％である、＜２＞～＜７＞のいずれか１つに記載の光硬化性組成物。
＜９＞　組成物におけるシロキサン結合濃度が、０．１００ｍｍｏｌ／ｇ～３．０００ｍｍｏｌ／ｇである、＜２＞～＜８＞のいずれか１つに記載の光硬化性組成物。
＜１０＞　前記（メタ）アクリルモノマー成分における芳香環濃度が、０．００１５ｍｏｌ／ｇ～０．００７０ｍｏｌ／ｇである、＜１＞～＜９＞のいずれか１つに記載の光硬化性組成物。
＜１１＞　前記（メタ）アクリルモノマー成分における芳香環濃度が０．００１５ｍｏｌ／ｇ～０．００４２ｍｏｌ／ｇである、＜１＞～＜９＞に記載の光硬化性組成物。
＜１２＞　前記（メタ）アクリルモノマー成分が、２つの（メタ）アクリロイルオキシ基と、芳香環とを有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離が、２５Å以上８０Å以下あるジ（メタ）アクリルモノマー（Ａ）を含む、＜１＞～１１＞のいずれか１つに記載の光硬化性組成物。
＜１３＞　以下の（ａ）及び（ｂ）のいずれかの条件を満たす、＜１＞～＜１２＞のいずれか１つに記載の光硬化性組成物。
　（ａ）前記（メタ）アクリルモノマー成分が、２つの（メタ）アクリロイルオキシ基と、芳香環とを有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離が、２５Å以上８０Å以下あるジ（メタ）アクリルモノマー（Ａ）を２種類以上含む。
　（ｂ）前記（メタ）アクリルモノマー成分が、
　２つの（メタ）アクリロイルオキシ基と、芳香環とを有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離が、２５Å以上８０Å以下あるジ（メタ）アクリルモノマー（Ａ）と、
　２つの（メタ）アクリロイルオキシ基と、芳香環及びウレタン結合の少なくとも一方と、を有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離が、１０Å以上２５Å未満であるジ（メタ）アクリルモノマー（Ｂ－１）、
　２つの（メタ）アクリロイルオキシ基と、芳香環及びウレタン結合の少なくとも一方と、を有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他
方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離が、８０Å超２００Å未満であるジ（メタ）アクリルモノマー（Ｂ－２）、及び
　１つの（メタ）アクリロイルオキシ基と、芳香環及びヒドロキシ基の少なくとも一方と、を有するモノ（メタ）アクリルモノマー（Ｂ－３）からなる群から選択される１つ以上の（メタ）アクリルモノマー（Ｂ）と、を含む。
＜１４＞　前記（ｂ）を満たし、かつ、
　前記（メタ）アクリルモノマー（Ｂ）が前記ジ（メタ）アクリルモノマー（Ｂ－１）を含む場合、前記ジ（メタ）アクリルモノマー（Ｂ－１）の分子量が４００以上８００以下であり、
　前記（メタ）アクリルモノマー（Ｂ）が前記ジ（メタ）アクリルモノマー（Ｂ－２）を含む場合、前記ジ（メタ）アクリルモノマー（Ｂ－２）の分子量が９００以上３０００以下であり、
　前記（メタ）アクリルモノマー（Ｂ）が前記モノ（メタ）アクリルモノマー（Ｂ－３）を含む場合、前記モノ（メタ）アクリルモノマー（Ｂ－３）の分子量が１３０以上３５０以下である、＜１３＞に記載の光硬化性組成物。
＜１５＞　前記（ｂ）を満たし、かつ、
　前記（メタ）アクリルモノマー（Ｂ）の含有量が、前記（メタ）アクリルモノマー成分の全量に対し、３質量％～８０質量％である、＜１３＞又は＜１４＞に記載の光硬化性組成物。
＜１６＞　前記ジ（メタ）アクリルモノマー（Ａ）の分子量が６５０以上１３００以下である、＜１２＞～＜１５＞のいずれか１つに記載の光硬化性組成物。
＜１７＞　前記ジ（メタ）アクリルモノマー（Ａ）の含有量が、前記（メタ）アクリルモノマー成分の全量に対し、３０質量％以上である、＜１２＞～＜１６＞のいずれか１つに記載の光硬化性組成物。
＜１８＞　Ｅ型粘度計により２５℃及び５０ｒｐｍの条件で測定される粘度が、５ｍＰａ・ｓ～６０００ｍＰａ・ｓである、＜１＞～＜１７＞のいずれか１つに記載の光硬化性組成物。
＜１９＞　光造形用の光硬化性組成物である、＜１＞～＜１８＞のいずれか１つに記載の光硬化性組成物。
＜２０＞　光造形による鋳型の製造に用いられる光硬化性組成物である、＜１＞～＜１９＞のいずれか１つに記載の光硬化性組成物。
＜２１＞　＜１＞～＜２０＞のいずれか１つに記載の光硬化性組成物の硬化物を含む、立体造形物。
＜２２＞　＜２１＞に記載の立体造形物を含む、鋳型。
＜２３＞　有床義歯の製造に用いられる、＜２２＞に記載の鋳型。
＜２４＞　＜２２＞又は＜２３＞に記載の鋳型内で硬化性組成物を重合させる工程を含む、硬化物の製造方法。
＜２５＞　光硬化性組成物を光造形により硬化させ、有床義歯の製造に用いられる鋳型を作製する工程と、
　前記鋳型内で硬化性組成物を重合させ、有床義歯を製造する工程と、を含む、有床義歯の製造方法。 Means for solving the above problems include the following aspects.
<1> A photocurable composition containing a (meth)acrylic monomer component and a photopolymerization initiator,
A cured layer A1 having a thickness of 50 μm is formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 , and by laminating the cured layer A1 in the thickness direction, the length A rectangular plate-shaped object A1 with a width of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet light with a wavelength of 365 nm at a dose of 3 J/cm 2 to form a long object. When a rectangular plate-shaped test piece A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was prepared,
The storage modulus of the test piece A1 at 25°C is 10 MPa or more,
A photocurable composition in which the storage modulus of the test piece A1 at 37° C. is 400 MPa or less.
<2> The (meth)acrylic monomer component is
A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring,
A di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and having no siloxane bond;
The photocurable composition according to <1>, comprising a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups.
<3> A photocurable composition comprising a (meth)acrylic monomer component and a photopolymerization initiator,
The (meth)acrylic monomer component is
A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring,
A di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and having no siloxane bond;
A photocurable composition comprising a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups.
<4> The photocurable composition according to <2> or <3>, wherein the di(meth)acrylic monomer (Y) has a molecular weight of 400 to 5,000.
<5> The photocurable composition according to any one of <2> to <4>, wherein the polyfunctional (meth)acrylic monomer (Z) has a molecular weight of 400 to 5,000.
<6> Any one of <2> to <5>, wherein the content of the mono(meth)acrylic monomer (X) is 30% by mass to 90% by mass with respect to the total amount of the (meth)acrylic monomer component. 1. The photocurable composition according to item 1.
<7> Any one of <2> to <6>, wherein the content of the di(meth)acrylic monomer (Y) is 5% by mass to 55% by mass with respect to the total amount of the (meth)acrylic monomer component. 1. The photocurable composition according to item 1.
<8> Any of <2> to <7>, wherein the content of the polyfunctional (meth)acrylic monomer (Z) is 1% by mass to 60% by mass with respect to the total amount of the (meth)acrylic monomer component. The photocurable composition according to item 1.
<9> The photocurable composition according to any one of <2> to <8>, wherein the siloxane bond concentration in the composition is 0.100 mmol/g to 3.000 mmol/g.
<10> The photocurable composition according to any one of <1> to <9>, wherein the (meth)acrylic monomer component has an aromatic ring concentration of 0.0015 mol/g to 0.0070 mol/g. .
<11> The photocurable composition according to <1> to <9>, wherein the (meth)acrylic monomer component has an aromatic ring concentration of 0.0015 mol/g to 0.0042 mol/g.
<12> The (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the Any one of <1> to 11>, comprising a di(meth)acrylic monomer (A) having a distance of 25 Å or more and 80 Å or less between the oxygen atom forming the oxy group in the (meth)acryloyloxy group The photocurable composition described in .
<13> The photocurable composition according to any one of <1> to <12>, which satisfies either of the following conditions (a) and (b).
(a) The (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the other Two or more types of di(meth)acrylic monomers (A) having a distance of 25 Å or more and 80 Å or less from the oxygen atom forming the oxy group in the (meth)acryloyloxy group are included.
(b) the (meth)acrylic monomer component is
It has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group forms the oxy group in the other (meth)acryloyloxy group. A di(meth)acrylic monomer (A) having a distance of 25 Å or more and 80 Å or less between the oxygen atom and
having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, an oxygen atom forming an oxy group in one (meth)acryloyloxy group, and the other (meth)acryloyloxy A di(meth)acrylic monomer (B-1) in which the distance between the oxygen atom forming the oxy group in the group is 10 Å or more and less than 25 Å,
having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, an oxygen atom forming an oxy group in one (meth)acryloyloxy group, and the other (meth)acryloyloxy A di(meth)acrylic monomer (B-2) in which the distance between the oxygen atom forming the oxy group in the group is more than 80 Å and less than 200 Å, and one (meth)acryloyloxy group and an aromatic ring and and one or more (meth)acrylic monomers (B) selected from the group consisting of mono(meth)acrylic monomers (B-3) having at least one hydroxy group.
<14> Satisfies the above (b), and
When the (meth)acrylic monomer (B) includes the di(meth)acrylic monomer (B-1), the molecular weight of the di(meth)acrylic monomer (B-1) is 400 or more and 800 or less,
When the (meth)acrylic monomer (B) includes the di(meth)acrylic monomer (B-2), the molecular weight of the di(meth)acrylic monomer (B-2) is 900 or more and 3000 or less,
When the (meth)acrylic monomer (B) includes the mono(meth)acrylic monomer (B-3), the molecular weight of the mono(meth)acrylic monomer (B-3) is 130 or more and 350 or less, <13 ＞The photocurable composition described in ＞.
<15> Satisfies the above (b), and
The photocurable composition according to <13> or <14>, wherein the content of the (meth)acrylic monomer (B) is 3% by mass to 80% by mass with respect to the total amount of the (meth)acrylic monomer component. thing.
<16> The photocurable composition according to any one of <12> to <15>, wherein the di(meth)acrylic monomer (A) has a molecular weight of 650 or more and 1300 or less.
<17> Any one of <12> to <16>, wherein the content of the di(meth)acrylic monomer (A) is 30% by mass or more based on the total amount of the (meth)acrylic monomer component. The photocurable composition described.
<18> The photocurable composition according to any one of <1> to <17>, which has a viscosity of 5 mPa·s to 6000 mPa·s as measured by an E-type viscometer at 25° C. and 50 rpm. thing.
<19> The photocurable composition according to any one of <1> to <18>, which is a photocurable composition for stereolithography.
<20> The photocurable composition according to any one of <1> to <19>, which is a photocurable composition used for manufacturing a mold by stereolithography.
<21> A three-dimensional object comprising a cured product of the photocurable composition according to any one of <1> to <20>.
<22> A mold including the three-dimensional structure according to <21>.
<23> The mold according to <22>, which is used for manufacturing a denture.
<24> A method for producing a cured product, comprising a step of polymerizing the curable composition in the mold according to <22> or <23>.
<25> A step of curing the photocurable composition by stereolithography to produce a mold used for manufacturing a denture,
A method for producing a denture with a denture, comprising the step of polymerizing a curable composition in the mold to produce a denture with a denture.
　本開示の一態様によれば、有床義歯の製造時における変形が抑制された鋳型又は鋳型を用いて有床義歯を製造する際に、鋳型内から有床義歯を取り出しやすい鋳型の作製が可能な光硬化性組成物、並びにこの光硬化性組成物を用いた立体造形物、鋳型、硬化物を製造する方法及び有床義歯の製造方法を提供される。
　本開示の他の一態様によれば、簡便な方法で有床義歯を作製可能である有床義歯の製造方法を提供される。 According to one aspect of the present disclosure, when producing a fixed denture using a mold or mold in which deformation during the production of a fixed denture is suppressed, it is possible to create a mold that allows easy removal of the fixed denture from within the mold. The present invention provides a photocurable composition, a method for producing a three-dimensional object, a mold, a cured product, and a method for producing a denture using the photocurable composition.
According to another aspect of the present disclosure, there is provided a method for manufacturing a denture that can be manufactured by a simple method.
実施例にて形成された立体造形物Ａ２の概略構成図である。FIG. 2 is a schematic configuration diagram of a three-dimensional structure A2 formed in an example. 実施例にて形成された立体造形物Ａ３の概略構成図である。FIG. 3 is a schematic configuration diagram of a three-dimensional structure A3 formed in an example. 実施例にて形成された立体造形物Ａ４の概略構成図である。FIG. 3 is a schematic configuration diagram of a three-dimensional structure A4 formed in an example.
　本開示において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　本開示において、組成物に含有される各成分の量は、組成物中に各成分に該当する物質が複数存在する場合は、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
　本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において、「光」は、紫外線、可視光線等の活性エネルギー線を包含する概念である。 In the present disclosure, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In the present disclosure, if there are multiple substances corresponding to each component in the composition, the amount of each component contained in the composition is the total amount of the multiple substances present in the composition, unless otherwise specified. means quantity.
In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. . Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
In the present disclosure, "light" is a concept that includes active energy rays such as ultraviolet rays and visible light.
　本開示において、「（メタ）アクリレート」はアクリレート又はメタクリレートを意味し、「（メタ）アクリロイル」はアクリロイル又はメタクリロイルを意味し、「（メタ）アクリル」はアクリル又はメタクリルを意味する。 In the present disclosure, "(meth)acrylate" means acrylate or methacrylate, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylic" means acrylic or methacrylic.
　以下、本開示の光硬化性組成物について、第１実施形態及び第２実施形態の光硬化性組成物について説明する。第１実施形態の好ましい形態及び第２実施形態の好ましい形態については、適宜組み合わせてもよい。第２実施形態の光硬化性組成物の好ましい用途及び物性は、別途言及がない限り、第１実施形態の光硬化性組成物の好ましい用途及び物性と同様である。 Hereinafter, regarding the photocurable composition of the present disclosure, the photocurable compositions of the first embodiment and the second embodiment will be described. The preferred embodiment of the first embodiment and the preferred embodiment of the second embodiment may be combined as appropriate. Preferred uses and physical properties of the photocurable composition of the second embodiment are the same as those of the photocurable composition of the first embodiment, unless otherwise mentioned.
［第１実施形態］
〔光硬化性組成物〕
　本開示の第１実施形態の光硬化性組成物は、（メタ）アクリルモノマー成分と、光重合開始剤と、を含む光硬化性組成物であって、
　前記光硬化性組成物に対し波長４０５ｎｍの可視光を照射量１１ｍＪ／ｃｍ２にて照射して厚み５０μｍの硬化層Ａ１を形成し、前記硬化層Ａ１を厚み方向に積層させることにより、長さ４０ｍｍ、幅１０ｍｍ、厚み１．０ｍｍの矩形板形状の造形物Ａ１を形成し、前記造形物Ａ１に対し、波長３６５ｎｍの紫外線を照射量３Ｊ／ｃｍ２にて照射する条件の光造形により、長さ４０ｍｍ、幅１０ｍｍ、厚み１．０ｍｍの矩形板形状の試験片Ａ１を作製した場合に、
　前記試験片Ａ１の２５℃における貯蔵弾性率が１０ＭＰａ以上であり、
　前記試験片Ａ１の３７℃における貯蔵弾性率が４００ＭＰａ以下である。 [First embodiment]
[Photocurable composition]
The photocurable composition of the first embodiment of the present disclosure is a photocurable composition containing a (meth)acrylic monomer component and a photopolymerization initiator,
A cured layer A1 having a thickness of 50 μm is formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 , and by laminating the cured layer A1 in the thickness direction, the length A rectangular plate-shaped object A1 with a width of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet light with a wavelength of 365 nm at a dose of 3 J/cm 2 to form a long object. When a rectangular plate-shaped test piece A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was prepared,
The storage modulus of the test piece A1 at 25°C is 10 MPa or more,
The storage modulus of the test piece A1 at 37° C. is 400 MPa or less.
　本開示の光硬化性組成物は、（メタ）アクリルモノマー成分と、光重合開始剤と、を含み、上記条件で作製した試験片Ａ１は、２５℃における貯蔵弾性率が１０ＭＰａ以上であり、かつ、試験片Ａ１の３７℃における貯蔵弾性率が４００ＭＰａ以下である。このような光硬化性組成物を用いることで、有床義歯の製造時における変形が抑制された鋳型又は鋳型を用いて有床義歯を製造する際に、鋳型内から有床義歯を取り出しやすい鋳型の作製が可能となる。 The photocurable composition of the present disclosure includes a (meth)acrylic monomer component and a photopolymerization initiator, and the test piece A1 prepared under the above conditions has a storage modulus of 10 MPa or more at 25°C, and , the storage modulus of test piece A1 at 37° C. is 400 MPa or less. By using such a photocurable composition, deformation during the production of dentures can be suppressed, or when manufacturing dentures using a mold, the dentures can be easily removed from the mold. It becomes possible to create
　本開示の光硬化性組成物は、光照射により硬化する組成物であり、この組成物を硬化させることで硬化物が得られる。本開示の光硬化性組成物を用いて硬化物を製造する際の製造方法は、光造形が好ましい。
　本開示の光硬化性組成物として、好ましくは、光造形用の光硬化性組成物であり、言い換えれば、本開示の光硬化性組成物を用いて製造される硬化物は、好ましくは光造形物（即ち、光造形による硬化物）である。 The photocurable composition of the present disclosure is a composition that is cured by light irradiation, and a cured product can be obtained by curing this composition. A preferred manufacturing method for manufacturing a cured product using the photocurable composition of the present disclosure is stereolithography.
The photocurable composition of the present disclosure is preferably a photocurable composition for stereolithography. In other words, the cured product produced using the photocurable composition of the present disclosure is preferably a photocurable composition for stereolithography. (i.e., a cured product obtained by stereolithography).
　光造形は、光硬化性組成物に光を照射して硬化層を形成する操作を繰り返すことにより、硬化層を積層させて硬化物（即ち、光造形物）を得る方法である。
　光造形としては、インクジェット方式の光造形であってもよく、液槽方式の光造形（即
ち、液槽を用いる光造形）であってもよい。 Stereolithography is a method of stacking cured layers to obtain a cured product (i.e., a stereolithography) by repeating the operation of irradiating a photocurable composition with light to form a cured layer.
The stereolithography may be an inkjet stereolithography or a liquid bath stereolithography (that is, stereolithography using a liquid tank).
　インクジェット方式の光造形では、インクジェットノズルから光硬化性組成物の液滴を基材に吐出し、基材に付着した液滴に光を照射することにより硬化物を得る。
　インクジェット方式の光造形の一例では、例えば、インクジェットノズル及び光源を備えるヘッドを平面内で走査させつつ、インクジェットノズルから光硬化性組成物を基材に吐出し、かつ、吐出された光硬化性組成物に光を照射して硬化層を形成し、これらの操作を繰り返して、硬化層を順次積層させて硬化物（即ち、光造形物）を得る。 In inkjet stereolithography, droplets of a photocurable composition are ejected from an inkjet nozzle onto a substrate, and the droplets adhering to the substrate are irradiated with light to obtain a cured product.
In an example of stereolithography using an inkjet method, for example, a head including an inkjet nozzle and a light source is scanned in a plane, and a photocurable composition is discharged from the inkjet nozzle onto a base material, and the discharged photocurable composition is A cured layer is formed by irradiating the object with light, and these operations are repeated to sequentially stack the cured layers to obtain a cured product (that is, a stereolithographic object).
　液槽方式の光造形では、液槽内に収容された光硬化性組成物（即ち、液体状態の未硬化の光硬化性組成物。以下同じ。）の一部を光照射によって硬化させて硬化層を形成し、この操作を繰り返すことで硬化層を積層させ、硬化物（即ち、光造形物）を得る。液槽方式の光造形は、液槽を用いる点で、インクジェット方式の光造形とは異なる。
　液槽方式の光造形としては、ＤＬＰ（Digital Light Processing）方式の光造形及びＳＬＡ（Stereolithography）方式の光造形が挙げられる。
　ＤＬＰ方式では、液槽内の光硬化性組成物に対し、面状の光を照射する。
　ＳＬＡ方式では、液槽内の光硬化性組成物に対し、レーザー光を走査する。
　本開示の光硬化性組成物による効果がより効果的に奏される観点から、液槽方式の光造形として、好ましくはＤＬＰ方式の光造形である。 In liquid bath method stereolithography, a part of the photocurable composition (i.e., an uncured photocurable composition in a liquid state; the same applies hereinafter) contained in a liquid bath is cured by light irradiation. By forming layers and repeating this operation, cured layers are laminated to obtain a cured product (that is, a stereolithographic product). Liquid bath type stereolithography differs from inkjet type stereolithography in that a liquid bath is used.
Examples of liquid bath type stereolithography include DLP (Digital Light Processing) type stereolithography and SLA (Stereolithography) type stereolithography.
In the DLP method, a planar light is irradiated onto the photocurable composition in a liquid tank.
In the SLA method, a photocurable composition in a liquid tank is scanned with a laser beam.
From the viewpoint of more effectively achieving the effects of the photocurable composition of the present disclosure, the liquid bath type stereolithography is preferably DLP type stereolithography.
　ＤＬＰ方式の光造形の一例では、例えば、
　鉛直方向に移動可能なビルドテーブルと、
　ビルドテーブルの下方（重力方向側。以下同じ。）に配置され、光透過性部を含み、光硬化性組成物が収容されるトレー（即ち、液槽）と、
　トレーの下方に配置され、トレー内の光硬化性組成物に対し、トレーの光透過性部を介して面状の光を照射するための光源（例えば、ＬＥＤ光源）と、
を備える３Ｄプリンタ（例えば、Ｋｕｌｚｅｒ社製の「Ｃａｒａ　Ｐｒｉｎｔ４．０」、Ａｓｉｇａ社製の「Ｍａｘ　ＵＶ」、等）が用いられる。
　この一例では、まず、ビルドテーブルとトレーとの間に一層分のギャップを設け、このギャップを、光硬化性組成物で満たす。次に、ギャップに満たされた光硬化性組成物に対し、下方から、トレーの光透過性部を介して面状の光を照射し、光が照射された領域を硬化させることにより、一層目の硬化層を形成する。次に、ビルドテーブルとトレーとのギャップを次の一層分広げ、生じた空間を光硬化性組成物で満たす。次に、空間に満たされた光硬化性組成物に対し、一層目の硬化と同様にして光を照射し、二層目の硬化層を形成する。以上の操作を繰り返すことにより、硬化層を積層させ、立体造形物を製造する。この一例において、製造された立体造形物に対し、さらに光を照射することにより、立体造形物をさらに硬化させてもよい。
　ＤＬＰ方式の光造形については、例えば、特許第５１１１８８０号公報及び特許第５２３５０５６号公報の記載を参照してもよい。 In an example of DLP stereolithography, for example,
A vertically movable build table,
A tray (i.e., a liquid tank) that is disposed below the build table (on the side in the gravity direction; the same applies hereinafter), includes a light-transmitting part, and contains a photocurable composition;
a light source (e.g., an LED light source) disposed below the tray for irradiating the photocurable composition in the tray with planar light through the light-transmitting part of the tray;
A 3D printer (for example, "Cara Print 4.0" manufactured by Kulzer, "Max UV" manufactured by Asiga, etc.) is used.
In this example, a one-layer gap is first created between the build table and the tray, and the gap is filled with a photocurable composition. Next, the photocurable composition filled in the gap is irradiated with planar light from below through the light-transmitting part of the tray, and the area irradiated with light is cured to form the first layer. form a hardened layer. The gap between the build table and the tray is then widened by the next layer and the resulting space is filled with the photocurable composition. Next, the photocurable composition filling the space is irradiated with light in the same manner as for curing the first layer to form a second cured layer. By repeating the above operations, the cured layers are laminated and a three-dimensional structure is manufactured. In this example, the manufactured three-dimensional structure may be further hardened by further irradiating the three-dimensional structure with light.
Regarding stereolithography using the DLP method, for example, the descriptions in Japanese Patent No. 5111880 and Japanese Patent No. 5235056 may be referred to.
＜用途＞
　本開示の光硬化性組成物の用途は特に制限されず、例えば、光造形による鋳型、歯科用製品等の製造に用いられる光硬化性組成物であることが好ましく、光造形による鋳型の製造に用いられる光硬化性組成物であることがより好ましい。 <Application>
The use of the photocurable composition of the present disclosure is not particularly limited, and for example, it is preferably a photocurable composition used for manufacturing molds, dental products, etc. by stereolithography, and is suitable for manufacturing molds by stereolithography. It is more preferable that the photocurable composition is used.
　鋳型としては、例えば、有床義歯の製造に用いられる鋳型が挙げられる。例えば、鋳型に人工歯を配列した状態で、義歯床作製用の硬化性組成物を鋳型に注入し、注入後の硬化性組成物を硬化させることで有床義歯を製造してもよい。 Examples of the mold include molds used for manufacturing dentures. For example, with artificial teeth arranged in a mold, a curable composition for making a denture base is injected into the mold, and the curable composition after injection is cured to produce a denture with a denture.
　歯科用製品としては、歯科用補綴物、口腔内で使用する医療器具、歯科用模型、消失鋳
造用模型、等が挙げられる。
　歯科用補綴物としては、インレー、クラウン、ブリッジ、テンポラリークラウン、テンポラリーブリッジ等が挙げられる。
　口腔内で使用する医療器具としては、デンチャー（例えば、コンプリートデンチャー（全部床義歯）、パーシャルデンチャー（部分床義歯）、等）、マウスピース、マウスガード、歯列矯正器具、咬合用スプリント、顎関節症治療用スプリント等のスプリント、印象採得用トレイ、手術用ガイド等が挙げられる。
　歯科用模型としては、歯顎モデル等が挙げられる。 Examples of dental products include dental prostheses, medical instruments used in the oral cavity, dental models, investment casting models, and the like.
Examples of dental prostheses include inlays, crowns, bridges, temporary crowns, and temporary bridges.
Medical devices used in the oral cavity include dentures (e.g., complete dentures, partial dentures, etc.), mouthpieces, mouth guards, orthodontic appliances, occlusal splints, and temporomandibular joints. Examples include splints such as splints for medical treatment, trays for impression taking, surgical guides, etc.
Examples of the dental model include a tooth and jaw model.
　本開示の光硬化性組成物では、試験片Ａ１の２５℃における貯蔵弾性率が１０ＭＰａ以上であり、鋳型の変形を抑制する観点（例えば、本開示の光硬化性組成物を用いて作製した鋳型に義歯床作製用等の光硬化性組成物を注入して重合する際の鋳型の変形を抑制する観点）から、１５ＭＰａ以上であることが好ましく、３０ＭＰａ以上であることがより好ましく、５０ＭＰａ以上であることがさらに好ましい。
　試験片Ａ１の２５℃における貯蔵弾性率の上限は特に限定されず、例えば、鋳型からの抜き出し性の観点（例えば、有床義歯を鋳型から抜き出す際の鋳型、有床義歯等の損傷を抑制する観点）から、２０００ＭＰａ以下であってもよく、１０００ＭＰａ以下であってもよく、５００ＭＰａ以下であってもよい。 In the photocurable composition of the present disclosure, the storage modulus of test piece A1 at 25° C. is 10 MPa or more, and from the viewpoint of suppressing mold deformation (for example, a mold made using the photocurable composition of the present disclosure). From the viewpoint of suppressing deformation of the mold when polymerizing by injecting a photocurable composition for denture base preparation, etc., the pressure is preferably 15 MPa or more, more preferably 30 MPa or more, and 50 MPa or more. It is even more preferable that there be.
The upper limit of the storage modulus of test piece A1 at 25°C is not particularly limited, and for example, from the viewpoint of ease of extraction from the mold (for example, to suppress damage to the mold, denture, etc. when pulling out the denture from the mold). viewpoint), the pressure may be 2000 MPa or less, 1000 MPa or less, or 500 MPa or less.
　本開示の光硬化性組成物では、試験片Ａ１の３７℃における貯蔵弾性率が４００ＭＰａ以下であり、鋳型からの抜き出し性の観点から、３００ＭＰａ以下であることが好ましく、２５０ＭＰａ以下であることがより好ましく、２００ＭＰａ以下であることがさらに好ましい。
　試験片Ａ１の３７℃における貯蔵弾性率の下限は特に限定されず、例えば、使用時の鋳型の変形を抑制する観点から、１０ＭＰａ以上であってもよく、３０ＭＰａ以上であってもよく、５０ＭＰａ以上であってもよい。 In the photocurable composition of the present disclosure, the storage modulus of test piece A1 at 37° C. is 400 MPa or less, and from the viewpoint of ease of extraction from the mold, it is preferably 300 MPa or less, and more preferably 250 MPa or less. It is preferably 200 MPa or less, and more preferably 200 MPa or less.
The lower limit of the storage modulus at 37°C of test piece A1 is not particularly limited, and for example, from the viewpoint of suppressing mold deformation during use, it may be 10 MPa or more, 30 MPa or more, 50 MPa or more. It may be.
　本開示の光硬化性組成物では、（メタ）アクリルモノマー成分における芳香環濃度が０．００１５ｍｏｌ／ｇ～０．００４２ｍｏｌ／ｇであることが好ましく、０．００１６ｍｏｌ／ｇ～０．００４１ｍｏｌ／ｇであることがより好ましく、０．００１７ｍｏｌ／ｇ～０．００４０ｍｏｌ／ｇであることがさらに好ましい。（メタ）アクリルモノマー成分における芳香環濃度を上記のように調整することで、鋳型からの抜き出し性により優れ、かつ使用時の鋳型の変形を好適に抑制できる傾向にある。 In the photocurable composition of the present disclosure, the aromatic ring concentration in the (meth)acrylic monomer component is preferably from 0.0015 mol/g to 0.0042 mol/g, and preferably from 0.0016 mol/g to 0.0041 mol/g. It is more preferable that the amount is 0.0017 mol/g to 0.0040 mol/g. By adjusting the aromatic ring concentration in the (meth)acrylic monomer component as described above, it tends to be easier to extract from the mold and to suitably suppress deformation of the mold during use.
　本開示の光硬化性組成物は、鋳型からの抜き出し性により優れ、かつ使用時の鋳型の変形を好適に抑制できる観点から、以下の（１）～（３）のいずれかの条件を満たすことが好ましい。
（１）（メタ）アクリルモノマー成分における芳香環濃度が０．００３０ｍｏｌ／ｇ～０．００４２ｍｏｌ／ｇである。
（２）（メタ）アクリルモノマー成分における芳香環濃度が０．００１５ｍｏｌ／ｇ～０．００３５ｍｏｌ／ｇであり、かつ、（メタ）アクリルモノマー成分におけるウレタン結合濃度が０．０００１ｍｏｌ／ｇ～０．００２０ｍｏｌ／ｇである。
（３）（メタ）アクリルモノマー成分における芳香環濃度が０．００１５ｍｏｌ／ｇ～０．００３５ｍｏｌ／ｇであり、かつ、（メタ）アクリルモノマー成分における水酸基濃度が０．０００５ｍｏｌ／ｇ～０．００３０ｍｏｌ／ｇである。 The photocurable composition of the present disclosure satisfies any of the following conditions (1) to (3) from the viewpoint of being superior in extractability from a mold and suitably suppressing mold deformation during use. is preferred.
(1) The aromatic ring concentration in the (meth)acrylic monomer component is 0.0030 mol/g to 0.0042 mol/g.
(2) The aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol/g to 0.0035 mol/g, and the urethane bond concentration in the (meth)acrylic monomer component is 0.0001 mol/g to 0.0020 mol /g.
(3) The aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol/g to 0.0035 mol/g, and the hydroxyl group concentration in the (meth)acrylic monomer component is 0.0005 mol/g to 0.0030 mol/g. It is g.
　（メタ）アクリルモノマー成分におけるウレタン結合濃度は、前述の（２）のように０．０００１ｍｏｌ／ｇ～０．００２０ｍｏｌ／ｇであってもよく、０．０００２ｍｏｌ／ｇ～０．００１８ｍｏｌ／ｇであってもよく、０．０００４ｍｏｌ／ｇ～０．００１６ｍｏｌ／ｇであってもよい。 The urethane bond concentration in the (meth)acrylic monomer component may be 0.0001 mol/g to 0.0020 mol/g, or 0.0002 mol/g to 0.0018 mol/g, as described in (2) above. It may be 0.0004 mol/g to 0.0016 mol/g.
　（メタ）アクリルモノマー成分における水酸基濃度は、前述の（３）のように０．０００５ｍｏｌ／ｇ～０．００３０ｍｏｌ／ｇであってもよく、０．０００６ｍｏｌ／ｇ～０．００２５ｍｏｌ／ｇであってもよく、０．０００８ｍｏｌ／ｇ～０．００２２ｍｏｌ／ｇであってもよい。 The hydroxyl group concentration in the (meth)acrylic monomer component may be 0.0005 mol/g to 0.0030 mol/g, or 0.0006 mol/g to 0.0025 mol/g, as described in (3) above. It may be 0.0008 mol/g to 0.0022 mol/g.
＜（メタ）アクリルモノマー成分＞
　本開示の光硬化性組成物は、（メタ）アクリルモノマー成分を少なくとも１種含む。 <(meth)acrylic monomer component>
The photocurable composition of the present disclosure includes at least one (meth)acrylic monomer component.
　硬化物における機械強度の観点から、本開示の光硬化性組成物の全量に対する（メタ）アクリルモノマー成分の含有量は、６０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。
　本開示の光硬化性組成物の全量に対する（メタ）アクリルモノマー成分の含有量の上限は特に限定されず、１００質量％未満であればよく、例えば、９９．９質量％以下であってもよい。 From the viewpoint of mechanical strength in the cured product, the content of the (meth)acrylic monomer component relative to the total amount of the photocurable composition of the present disclosure is preferably 60% by mass or more, more preferably 80% by mass or more. It is preferably 90% by mass or more, and more preferably 90% by mass or more.
The upper limit of the content of the (meth)acrylic monomer component relative to the total amount of the photocurable composition of the present disclosure is not particularly limited, and may be less than 100% by mass, for example, may be 99.9% by mass or less. .
　ここで、（メタ）アクリルモノマー成分とは、分子中に１つ以上の（メタ）アクリロイルオキシ基を有するモノマーを意味する。 Here, the (meth)acrylic monomer component means a monomer having one or more (meth)acryloyloxy groups in the molecule.
　本開示の光硬化性組成物は、（メタ）アクリルモノマー成分以外の光重合性成分を含んでいてもよく、含んでいなくてもよい。
　（メタ）アクリルモノマー成分以外の光重合性成分としては、スチレン、スチレン誘導体、（メタ）アクリロニトリル、等が挙げられる。
　本開示の光硬化性組成物では、（メタ）アクリルモノマー成分以外の光重合性成分の含有量は、本開示の光硬化性組成物中の光重合性成分の全量に対し、２０質量％以下であってもよく、１０質量％以下であってもよく、５質量％以下であってもよく、１．０質量％以下であってもよい。
　（メタ）アクリルモノマー成分以外の光重合性成分の含有量の下限は特に限定されず、例えば、０質量％以上であってもよい。 The photocurable composition of the present disclosure may or may not contain photopolymerizable components other than the (meth)acrylic monomer component.
Examples of photopolymerizable components other than the (meth)acrylic monomer component include styrene, styrene derivatives, (meth)acrylonitrile, and the like.
In the photocurable composition of the present disclosure, the content of photopolymerizable components other than the (meth)acrylic monomer component is 20% by mass or less based on the total amount of photopolymerizable components in the photocurable composition of the present disclosure. It may be 10% by mass or less, 5% by mass or less, or 1.0% by mass or less.
The lower limit of the content of photopolymerizable components other than the (meth)acrylic monomer component is not particularly limited, and may be, for example, 0% by mass or more.
　（メタ）アクリルモノマー成分を構成する（メタ）アクリルモノマーとしては、分子中に１つ以上の（メタ）アクリロイルオキシ基を有するモノマーであればよく、その他には特に制限はない。
　（メタ）アクリルモノマーは、単官能（メタ）アクリルモノマー（即ち、分子中に１つの（メタ）アクリロイルオキシ基を有するモノマー）であっても、２官能（メタ）アクリルモノマー（即ち、分子中に２つの（メタ）アクリロイルオキシ基を有するモノマー）であっても、多官能（メタ）アクリルモノマー（即ち、３官能以上の（メタ）アクリルモノマー；即ち、分子中に３つ以上の（メタ）アクリロイルオキシ基を有するモノマー）であってもよい。 The (meth)acrylic monomer constituting the (meth)acrylic monomer component is not particularly limited as long as it is a monomer having one or more (meth)acryloyloxy groups in the molecule.
A (meth)acrylic monomer may be a monofunctional (meth)acrylic monomer (i.e., a monomer having one (meth)acryloyloxy group in the molecule) or a difunctional (meth)acrylic monomer (i.e., a monomer having one (meth)acryloyloxy group in the molecule). Even if the monomer has two (meth)acryloyloxy groups), it is a polyfunctional (meth)acrylic monomer (i.e., a trifunctional or more functional (meth)acrylic monomer; i.e., a monomer with three or more (meth)acryloyl groups in the molecule. A monomer having an oxy group) may also be used.
　（メタ）アクリルモノマー成分は、試験片Ａ１の２５℃における貯蔵弾性率及び３７℃における貯蔵弾性率を低下させる観点から、２つの（メタ）アクリロイルオキシ基と、芳香環とを有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離（以下、距離ｄ１とも称する。）が、２５Å以上８０Å以下あるジ（メタ）アクリルモノマー（Ａ）を含むことが好ましい。
　（メタ）アクリルモノマー成分は、ジ（メタ）アクリルモノマー（Ａ）を１種単独で含んでいてもよく、２種以上含んでいてもよい。 The (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and one The distance between an oxygen atom forming an oxy group in a (meth)acryloyloxy group and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group (hereinafter also referred to as distance d1) is , preferably contains a di(meth)acrylic monomer (A) having a thickness of 25 Å or more and 80 Å or less.
The (meth)acrylic monomer component may contain one type of di(meth)acrylic monomer (A) alone, or may contain two or more types of di(meth)acrylic monomer (A).
　本開示において、ｄ１（即ち、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離）は、これら２つの酸素原子間の直線距離を意味する。
　ｄ１は、パーキンエルマー社製の「Ｃｈｅｍ　３Ｄ」（バージョン１８．２．０．４８）における「ｄｉｓｐｌａｙ　ｄｉｓｔａｎｃｅ　ｍｅａｓｕｒｅｍｅｎｔ」機能を用いて求められる値を意味する。 In the present disclosure, d1 (i.e., the distance between the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the oxygen atom forming the oxy group in the other (meth)acryloyloxy group) ) means the straight line distance between these two oxygen atoms.
d1 means a value determined using the "display distance measurement" function in "Chem 3D" (version 18.2.0.48) manufactured by PerkinElmer.
　ジ（メタ）アクリルモノマー（Ａ）のｄ１は、２５Å以上８０Å以下であり、例えば、３０Å以上６０Å以下であってもよく、３０Å以上５０Å以下であってもよい。 The d1 of the di(meth)acrylic monomer (A) is 25 Å or more and 80 Å or less, for example, may be 30 Å or more and 60 Å or less, or may be 30 Å or more and 50 Å or less.
　ジ（メタ）アクリルモノマー（Ａ）は、環状構造を含むことが好ましい。環状構造としては、芳香族構造、脂環式構造等が挙げられる。中でも、ジ（メタ）アクリルモノマー（Ａ）は、芳香族構造を含むことが好ましく、ビスフェノールＡ、ビスフェノールＦ等のビスフェノール構造を含むことが好ましい。 It is preferable that the di(meth)acrylic monomer (A) contains a cyclic structure. Examples of the cyclic structure include an aromatic structure and an alicyclic structure. Among these, the di(meth)acrylic monomer (A) preferably contains an aromatic structure, and preferably contains a bisphenol structure such as bisphenol A and bisphenol F.
　ジ（メタ）アクリルモノマー（Ａ）は、エチレンオキシ基及びプロピレンオキシ基の少なくとも一方を有していてもよい。 The di(meth)acrylic monomer (A) may have at least one of an ethyleneoxy group and a propyleneoxy group.
　ジ（メタ）アクリルモノマー（Ａ）の分子量は、６５０以上１３００以下であることが好ましく、７００以上１２００以下であることがより好ましく、７５０以上１０００以下であることがさらに好ましい。 The molecular weight of the di(meth)acrylic monomer (A) is preferably 650 or more and 1,300 or less, more preferably 700 or more and 1,200 or less, and even more preferably 750 or more and 1,000 or less.
　ジ（メタ）アクリルモノマー（Ａ）の重量平均分子量は、６５０以上１３００以下であることが好ましく、７００以上１２００以下であることがより好ましく、７５０以上１０００以下であることがさらに好ましい。
　本開示において、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって測定される。 The weight average molecular weight of the di(meth)acrylic monomer (A) is preferably 650 or more and 1,300 or less, more preferably 700 or more and 1,200 or less, and even more preferably 750 or more and 1,000 or less.
In this disclosure, weight average molecular weight is measured by gel permeation chromatography (GPC).
　ジ（メタ）アクリルモノマー（Ａ）としては、エトキシ化ビスフェノールＡジ（メタ）アクリレート、プロポキシ化ビスフェノールＡジ（メタ）アクリレート、エトキシ化ビスフェノールＦジ（メタ）アクリレート、プロポキシ化ビスフェノールＦジ（メタ）アクリレート等が挙げられる。 As the di(meth)acrylic monomer (A), ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, propoxylated bisphenol F di(meth)acrylate, Examples include acrylate.
　ジ（メタ）アクリルモノマー（Ａ）の含有量は、（メタ）アクリルモノマー成分の全量に対し、３０質量％以上であることが好ましく、４０質量％～１００質量％であることがより好ましく、５０質量％～１００質量％であることがさらに好ましい。 The content of the di(meth)acrylic monomer (A) is preferably 30% by mass or more, more preferably 40% to 100% by mass, and 50% by mass or more based on the total amount of the (meth)acrylic monomer component. More preferably, the amount is from % by mass to 100% by mass.
　（メタ）アクリルモノマー成分は、抜き出し性を確保しやすく、かつ変形を抑制しやすい鋳型の形成がより容易となる観点から、以下の（ａ）及び（ｂ）のいずれかの条件を満たすことが好ましい。
　（ａ）（メタ）アクリルモノマー成分が、前述のジ（メタ）アクリルモノマー（Ａ）を２種類以上含む。
　（ｂ）（メタ）アクリルモノマー成分が、
　前述のジ（メタ）アクリルモノマー（Ａ）と、
　２つの（メタ）アクリロイルオキシ基と、芳香環及びウレタン結合の少なくとも一方と、を有し、距離ｄ１が、１０Å以上２５Å未満であるジ（メタ）アクリルモノマー（Ｂ－１）、
　２つの（メタ）アクリロイルオキシ基と、芳香環及びウレタン結合の少なくとも一方と、を有し、距離ｄ１が、８０Å超２００Å未満であるジ（メタ）アクリルモノマー（Ｂ－２）、及び
　１つの（メタ）アクリロイルオキシ基と、芳香環及びヒドロキシ基の少なくとも一方と、を有するモノ（メタ）アクリルモノマー（Ｂ－３）からなる群から選択される１つ以上の（メタ）アクリルモノマー（Ｂ）と、を含む。 The (meth)acrylic monomer component should satisfy either of the following conditions (a) and (b) from the viewpoint of making it easier to form a mold that can easily ensure extractability and easily suppress deformation. preferable.
(a) The (meth)acrylic monomer component contains two or more types of the aforementioned di(meth)acrylic monomers (A).
(b) The (meth)acrylic monomer component is
The aforementioned di(meth)acrylic monomer (A),
A di(meth)acrylic monomer (B-1) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and a distance d1 of 10 Å or more and less than 25 Å,
A di(meth)acrylic monomer (B-2) having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and having a distance d1 of more than 80 Å and less than 200 Å, and one ( one or more (meth)acrylic monomers (B) selected from the group consisting of mono(meth)acrylic monomers (B-3) having a meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group; ,including.
　（メタ）アクリルモノマー成分が前述の（ａ）を満たす場合、（メタ）アクリルモノマー成分は、２種以上のジ（メタ）アクリルモノマー（Ａ）を含んでいればよく、その他の（メタ）アクリルモノマー成分を含んでいてもよく、含んでいなくてもよい。
　（メタ）アクリルモノマー成分は、２種以上のジ（メタ）アクリルモノマー（Ａ）を含むことで、試験片Ａ１の２５℃における貯蔵弾性率及び３７℃における貯蔵弾性率を低下させるだけでなく、１種類のジ（メタ）アクリルモノマー（Ａ）を使用する場合より反応性を制御しやすくなり、光造形時における操作性に優れる。 When the (meth)acrylic monomer component satisfies the above (a), the (meth)acrylic monomer component only needs to contain two or more types of di(meth)acrylic monomers (A), and other (meth)acrylic It may or may not contain a monomer component.
By containing two or more types of di(meth)acrylic monomers (A), the (meth)acrylic monomer component not only lowers the storage modulus at 25°C and the storage modulus at 37°C of test piece A1, but also It is easier to control the reactivity than when one type of di(meth)acrylic monomer (A) is used, and the operability during stereolithography is excellent.
　（メタ）アクリルモノマー成分が前述の（ａ）を満たす場合、ジ（メタ）アクリルモノマー（Ａ）の合計含有量は、（メタ）アクリルモノマー成分の全量に対し、５０質量％～１００質量％であることが好ましく、７０質量％～１００質量％であることがより好ましく、９０質量％～１００質量％であることがさらに好ましい。 When the (meth)acrylic monomer component satisfies the above (a), the total content of the di(meth)acrylic monomer (A) is 50% by mass to 100% by mass based on the total amount of the (meth)acrylic monomer component. It is preferably from 70% by mass to 100% by mass, even more preferably from 90% by mass to 100% by mass.
　（メタ）アクリルモノマー成分が前述の（ｂ）を満たす場合、（メタ）アクリルモノマー成分は、前述のジ（メタ）アクリルモノマー（Ａ）と、（メタ）アクリルモノマー（Ｂ）とを含む。このとき、（メタ）アクリルモノマー成分は、ジ（メタ）アクリルモノマー（Ａ）及び（メタ）アクリルモノマーをそれぞれ独立に１種単独で含んでいてもよく、２種以上含んでいてもよい。
　以下、（メタ）アクリルモノマー（Ｂ）に分類されるジ（メタ）アクリルモノマー（Ｂ－１）、ジ（メタ）アクリルモノマー（Ｂ－２）及びモノ（メタ）アクリルモノマー（Ｂ－３）の詳細について説明する。 When the (meth)acrylic monomer component satisfies the above-mentioned (b), the (meth)acrylic monomer component contains the above-mentioned di(meth)acrylic monomer (A) and (meth)acrylic monomer (B). At this time, the (meth)acrylic monomer component may each independently contain one type of di(meth)acrylic monomer (A) and (meth)acrylic monomer, or may contain two or more types thereof.
Below, di(meth)acrylic monomer (B-1), di(meth)acrylic monomer (B-2) and mono(meth)acrylic monomer (B-3) classified as (meth)acrylic monomer (B) are I will explain the details.
≪ジ（メタ）アクリルモノマー（Ｂ－１）≫
　ジ（メタ）アクリルモノマー（Ｂ－１）は、２つの（メタ）アクリロイルオキシ基と、芳香環及びウレタン結合の少なくとも一方と、を有し、距離ｄ１が、１０Å以上２５Å未満である（メタ）アクリルモノマー成分である。ジ（メタ）アクリルモノマー（Ｂ－１）を用いることで、試験片Ａ１の２５℃における貯蔵弾性率及び３７℃における貯蔵弾性率を増加させる傾向にある。 ≪Di(meth)acrylic monomer (B-1)≫
The di(meth)acrylic monomer (B-1) has two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and the distance d1 is 10 Å or more and less than 25 Å (meth) It is an acrylic monomer component. The use of di(meth)acrylic monomer (B-1) tends to increase the storage modulus at 25°C and the storage modulus at 37°C of test piece A1.
　ジ（メタ）アクリルモノマー（Ｂ－１）のｄ１は、１２Å以上２４Å以下であってもよく、１４Å以上２２Å以下であってもよい。 d1 of the di(meth)acrylic monomer (B-1) may be 12 Å or more and 24 Å or less, or 14 Å or more and 22 Å or less.
　ジ（メタ）アクリルモノマー（Ｂ－１）の分子量は、４００以上８００以下であることが好ましく、４００以上７００以下であることがより好ましく、４００以上６５０以下であることがさらに好ましい。 The molecular weight of the di(meth)acrylic monomer (B-1) is preferably 400 or more and 800 or less, more preferably 400 or more and 700 or less, and even more preferably 400 or more and 650 or less.
　ジ（メタ）アクリルモノマー（Ｂ－１）の重量平均分子量は、４００以上８００以下であることが好ましく、４００以上７００以下であることがより好ましく、４００以上６５０以下であることがさらに好ましい。 The weight average molecular weight of the di(meth)acrylic monomer (B-1) is preferably 400 or more and 800 or less, more preferably 400 or more and 700 or less, and even more preferably 400 or more and 650 or less.
　ジ（メタ）アクリルモノマー（Ｂ－１）は、芳香環及びウレタン結合の少なくとも一方と、を有する。ジ（メタ）アクリルモノマー（Ｂ－１）は、芳香環及びウレタン結合の一方のみを含んでいてもよく、芳香環及びウレタン結合の両方を含んでいてもよい。 The di(meth)acrylic monomer (B-1) has at least one of an aromatic ring and a urethane bond. The di(meth)acrylic monomer (B-1) may contain only one of an aromatic ring and a urethane bond, or may contain both an aromatic ring and a urethane bond.
　ジ（メタ）アクリルモノマー（Ｂ－１）が芳香環を含み、ウレタン結合を含まない場合、ジ（メタ）アクリルモノマー（Ｂ－１）は、エチレンオキシ基及びプロピレンオキシ基の少なくとも一方を有していてもよく、ジ（メタ）アクリルモノマー（Ｂ－１）は、ビスフェノール構造と、エチレンオキシ基及びプロピレンオキシ基の少なくとも一方と、を有していてもよい。 When the di(meth)acrylic monomer (B-1) contains an aromatic ring and does not contain a urethane bond, the di(meth)acrylic monomer (B-1) has at least one of an ethyleneoxy group and a propyleneoxy group. The di(meth)acrylic monomer (B-1) may have a bisphenol structure and at least one of an ethyleneoxy group and a propyleneoxy group.
　ジ（メタ）アクリルモノマー（Ｂ－１）が芳香環を含み、ウレタン結合を含まない場合、ジ（メタ）アクリルモノマー（Ｂ－１）の具体例としては、エトキシ化ビスフェノールＡジ（メタ）アクリレート、プロポキシ化ビスフェノールＡジ（メタ）アクリレート、エトキシ化ビスフェノールＦジ（メタ）アクリレート、プロポキシ化ビスフェノールＦジ（メタ）アクリレート等が挙げられる。 When the di(meth)acrylic monomer (B-1) contains an aromatic ring and does not contain a urethane bond, specific examples of the di(meth)acrylic monomer (B-1) include ethoxylated bisphenol A di(meth)acrylate , propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, propoxylated bisphenol F di(meth)acrylate, and the like.
　ジ（メタ）アクリルモノマー（Ｂ－１）がウレタン結合を含む場合、下記式（１）で表
される化合物を含んでいてもよい。 When the di(meth)acrylic monomer (B-1) contains a urethane bond, it may contain a compound represented by the following formula (1).
　式（１）中、Ｒ１は、２価の鎖状炭化水素基であり、
　Ｒ２及びＲ３は、それぞれ独立に、置換基を有してもよい２価の鎖状炭化水素基であり、
　Ｒ４及びＲ５は、それぞれ独立に、メチル基又は水素原子である。 In formula (1), R 1 is a divalent chain hydrocarbon group,
R 2 and R 3 are each independently a divalent chain hydrocarbon group which may have a substituent,
R 4 and R 5 are each independently a methyl group or a hydrogen atom.
　式（１）中のＲ１において、２価の鎖状炭化水素基の炭素数としては、１～２０が好ましく、１～１０がより好ましく、２～６がさらに好ましい。
　Ｒ１における２価の鎖状炭化水素基は、直鎖状であっても分岐鎖状であってもよく、飽和でも不飽和でもよく、置換基を有していてもよい。
　Ｒ１における２価の鎖状炭化水素基として、好ましくは炭素数１～２０の直鎖又は分岐鎖アルキレン基であり、より好ましくは炭素数１～１２の直鎖又は分岐鎖アルキレン基であり、さらに好ましくは炭素数１～１０の直鎖又は分岐鎖アルキレン基である。 In R 1 in formula (1), the number of carbon atoms in the divalent chain hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 2 to 6.
The divalent chain hydrocarbon group in R 1 may be linear or branched, saturated or unsaturated, and may have a substituent.
The divalent chain hydrocarbon group in R 1 is preferably a straight chain or branched alkylene group having 1 to 20 carbon atoms, more preferably a straight chain or branched alkylene group having 1 to 12 carbon atoms, More preferably, it is a straight chain or branched alkylene group having 1 to 10 carbon atoms.
　上記炭素数１～２０の直鎖状又は分岐鎖状アルキレン基の具体例として、例えば、メチレン基、エチレン基、プロパンジイル基、ブタンジイル基、ペンタンジイル基、ヘキサンジイル基、ヘプタンジイル基、オクタンジイル基、ノナンジイル基、デカンジイル基、ウンデカンジイル基、ドデカンジイル基、トリデカンジイル基、テトラデカンジイル基、ペンタデカンジイル基、オクタデカンジイル基、エイコシレン基、ビニレン基、プロペンジイル基、ブテンジイル基、ペンテンジイル基、エチニレン基、プロピニレン、２，４，４－トリメチルヘキシレン基が挙げられる。これらのうち、ヘキサンジイル基、２，４，４－トリメチルヘキシレン基が好ましい。 Specific examples of the linear or branched alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, decanediyl group, undecanediyl group, dodecanediyl group, tridecanediyl group, tetradecanediyl group, pentadecanediyl group, octadecanediyl group, eicosylene group, vinylene group, propendiyl group, butenediyl group, pentendiyl group, ethynylene group, propynylene, A 2,4,4-trimethylhexylene group is mentioned. Among these, hexanediyl group and 2,4,4-trimethylhexylene group are preferred.
　式（１）において、Ｒ２及びＲ３は、それぞれ独立に、置換基を有してもよい２価の鎖状炭化水素基である。
　Ｒ２及びＲ３として好適な２価の鎖状炭化水素基は、Ｒ１として好適な２価の鎖状炭化水素基と同様である。
　ただし、Ｒ２及びＲ３における、置換基を有してもよい２価の鎖状炭化水素基の炭素数は、２～６であることが好ましく、２～３であることがより好ましい。 In formula (1), R 2 and R 3 each independently represent a divalent chain hydrocarbon group which may have a substituent.
The divalent chain hydrocarbon groups suitable as R 2 and R 3 are the same as the divalent chain hydrocarbon groups suitable as R 1 .
However, the number of carbon atoms in the divalent chain hydrocarbon group which may have a substituent in R 2 and R 3 is preferably 2 to 6, more preferably 2 to 3.
　Ｒ２及びＲ３が、置換基を有する２価の鎖状炭化水素基である場合の上記置換基としては、例えば；
メチル基、エチル基などの炭素数１～６のアルキル基；
アリール基；
シクロペンチル基、シクロヘキシル基などの炭素数３～６のシクロアルキル基；
トリル基；
キシリル基；
クミル基；
スチリル基；
メトキシフェニル基、エトキシフェニル基、プロポキシフェニル基などのアルコキシフェニル基；
フェノキシメチル基、フェノキシエチル基、フェノキシプロピル基などのフェノキシアルキル基等が挙げられる。 When R 2 and R 3 are divalent chain hydrocarbon groups having a substituent, examples of the substituent include;
an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group;
Aryl group;
Cycloalkyl groups having 3 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group;
tolyl group;
xylyl group;
Cumyl group;
Styryl group;
Alkoxyphenyl groups such as methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group;
Examples include phenoxyalkyl groups such as phenoxymethyl group, phenoxyethyl group, and phenoxypropyl group.
≪ジ（メタ）アクリルモノマー（Ｂ－２）≫
　ジ（メタ）アクリルモノマー（Ｂ－２）は、２つの（メタ）アクリロイルオキシ基と、芳香環及びウレタン結合の少なくとも一方と、を有し、距離ｄ１が、８０Å超２００Å未満である（メタ）アクリルモノマー成分である。ジ（メタ）アクリルモノマー（Ｂ－２）を用いることで、試験片Ａ１の２５℃における貯蔵弾性率及び３７℃における貯蔵弾性率を減少させる傾向にある。 ≪Di(meth)acrylic monomer (B-2)≫
The di(meth)acrylic monomer (B-2) has two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and the distance d1 is more than 80 Å and less than 200 Å (meth) It is an acrylic monomer component. The use of di(meth)acrylic monomer (B-2) tends to reduce the storage modulus at 25°C and the storage modulus at 37°C of test piece A1.
　ジ（メタ）アクリルモノマー（Ｂ－２）のｄ１は、８５Å以上１５０Å以下であってもよく、９０Å以上１２０Å以下であってもよい。 d1 of the di(meth)acrylic monomer (B-2) may be 85 Å or more and 150 Å or less, or 90 Å or more and 120 Å or less.
　ジ（メタ）アクリルモノマー（Ｂ－２）の分子量は、９００以上３０００以下であることが好ましく、１２００以上２５００以下であることがより好ましく、１５００以上２０００以下であることがさらに好ましい。 The molecular weight of the di(meth)acrylic monomer (B-2) is preferably 900 or more and 3000 or less, more preferably 1200 or more and 2500 or less, and even more preferably 1500 or more and 2000 or less.
　ジ（メタ）アクリルモノマー（Ｂ－２）の重量平均分子量は、９００以上３０００以下であることが好ましく、１２００以上２５００以下であることがより好ましく、１５００以上２０００以下であることがさらに好ましい。 The weight average molecular weight of the di(meth)acrylic monomer (B-2) is preferably 900 or more and 3000 or less, more preferably 1200 or more and 2500 or less, and even more preferably 1500 or more and 2000 or less.
　ジ（メタ）アクリルモノマー（Ｂ－２）は、芳香環及びウレタン結合の少なくとも一方と、を有する。ジ（メタ）アクリルモノマー（Ｂ－１）は、芳香環及びウレタン結合の一方のみを含んでいてもよく、芳香環及びウレタン結合の両方を含んでいてもよい。 The di(meth)acrylic monomer (B-2) has at least one of an aromatic ring and a urethane bond. The di(meth)acrylic monomer (B-1) may contain only one of an aromatic ring and a urethane bond, or may contain both an aromatic ring and a urethane bond.
　ジ（メタ）アクリルモノマー（Ｂ－２）がウレタン結合を含む場合、下記式（２）で表される化合物を含んでいてもよい。 When the di(meth)acrylic monomer (B-2) contains a urethane bond, it may contain a compound represented by the following formula (2).
　式（２）中、Ｒ６は、それぞれ独立に、２価の鎖状炭化水素基、芳香族構造を有する２価の炭化水素基、又は脂環式構造を有する２価の炭化水素基であり、
　Ｒ７は、それぞれ独立に、置換基を有してもよい２価の鎖状炭化水素基であり、
　Ｒ８は、２価の連結基であり、
　Ｒ９及びＲ１０は、それぞれ独立に、メチル基又は水素原子である。 In formula (2), R 6 is each independently a divalent chain hydrocarbon group, a divalent hydrocarbon group having an aromatic structure, or a divalent hydrocarbon group having an alicyclic structure. ,
R 7 is each independently a divalent chain hydrocarbon group which may have a substituent,
R 8 is a divalent linking group,
R 9 and R 10 are each independently a methyl group or a hydrogen atom.
　式（２）中、Ｒ６が２価の鎖状炭化水素基である場合、Ｒ６の好ましい構成は、式（１）中のＲ１の好ましい構成と同様である。 In formula (2), when R 6 is a divalent chain hydrocarbon group, the preferred configuration of R 6 is the same as the preferred configuration of R 1 in formula (1).
　式（２）中のＲ６において、芳香族構造を有する２価の炭化水素基としては、置換基を有していてもよい炭素数６～２０（より好ましくは炭素数６～１２、さらに好ましくは炭素数６～１０）の芳香族構造を有する２価の炭化水素基であることが好ましい。
　芳香族構造を有する２価の炭化水素基の例としては、アリーレン基、アルキレンアリーレン基、アルキレンアリーレンアルキレン基、及びアリーレンアルキレンアリーレン基を挙げることができる。
　芳香族構造を有する２価の炭化水素基としては、アルキレンアリーレン基又はアルキレンアリーレンアルキレン基であることが好ましい。 In R 6 in formula (2), the divalent hydrocarbon group having an aromatic structure has 6 to 20 carbon atoms (more preferably 6 to 12 carbon atoms, even more preferably 6 to 12 carbon atoms, and even more preferably 6 to 12 carbon atoms), which may have a substituent. is preferably a divalent hydrocarbon group having an aromatic structure and having 6 to 10 carbon atoms.
Examples of the divalent hydrocarbon group having an aromatic structure include an arylene group, an alkylenearylene group, an alkylenearylenealkylene group, and an arylenealkylenearylene group.
The divalent hydrocarbon group having an aromatic structure is preferably an alkylenearylene group or an alkylenearylenealkylene group.
　アリーレン基、アルキレンアリーレン基、アルキレンアリーレンアルキレン基、アルキルアリーレン基及びアリーレンアルキレンアリーレン基の具体例としては、１，３－又は１，４－フェニレン基、１，３－又は１，４－フェニレンジメチレン基、及び１，３－又は１，４－フェニレンジエチレン基が挙げられる。 Specific examples of the arylene group, alkylenearylene group, alkylenearylenealkylene group, alkylarylene group and arylenealkylenearylene group include 1,3- or 1,4-phenylene group, 1,3- or 1,4-phenylene dimethylene group and 1,3- or 1,4-phenylene diethylene groups.
　式（２）のＲ６において、脂環式構造を有する２価の炭化水素基としては、炭素数３～２０であることが好ましく、６～１２であることがより好ましく、６～８であることがさらに好ましい。 In R 6 of formula (2), the divalent hydrocarbon group having an alicyclic structure preferably has 3 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and more preferably 6 to 8 carbon atoms. It is even more preferable.
　脂環式構造としては、例えば、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロへキシレン基、シクロヘキセニレン基、シクロヘプチレン基、シクロオクチレン基、シクロノニレン基、シクロデシレン基、シクロウンデシレン基、シクロドデシレン基、シクロトリデシレン基、シクロテトラデシレン基、シクロペンタデシレン基、シクロオクタデシレン基、シクロイコシレン基、ビシクロへキシレン基、ノルボルニレン基、イソボルニレン基、アダマンチレン基、メチレンビスシクロへキシレン基等が挙げられる。 Examples of the alicyclic structure include cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclohexenylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group, Cyclododecylene group, cyclotridecylene group, cyclotetradecylene group, cyclopentadecylene group, cyclooctadecylene group, cycloicosylene group, bicyclohexylene group, norbornylene group, isobornylene group, adamantylene group, methylenebiscyclo Examples include xylene group.
　式（２）中のＲ６における脂環式構造を有する２価の炭化水素基は、置換基を有していてもよい。置換基としては、炭素数１～６の直鎖又は分岐鎖アルキル基が挙げられる。 The divalent hydrocarbon group having an alicyclic structure in R 6 in formula (2) may have a substituent. Examples of the substituent include straight chain or branched alkyl groups having 1 to 6 carbon atoms.
　式（２）中、Ｒ７の好ましい構成は、式（１）中のＲ２及びＲ３の好ましい構成と同様である。
　式（２）中、Ｒ８は２価の連結基である。２価の連結基としては、例えば、ポリエーテル基、アルキレン基、アリーレン基、アルキレンアリーレン基、アルキレンアリーレンアルキレン基等が挙げられる。中でも、ポリエーテル基が好ましく、炭素数２～４のエーテル基により構成されるポリエーテル基がより好ましい。 In formula (2), the preferred configuration of R 7 is the same as the preferred configuration of R 2 and R 3 in formula (1).
In formula (2), R 8 is a divalent linking group. Examples of the divalent linking group include a polyether group, an alkylene group, an arylene group, an alkylenearylene group, an alkylenearylenealkylene group, and the like. Among these, polyether groups are preferred, and polyether groups constituted by ether groups having 2 to 4 carbon atoms are more preferred.
≪モノ（メタ）アクリルモノマー（Ｂ－３）≫
　モノ（メタ）アクリルモノマー（Ｂ－３）は、１つの（メタ）アクリロイルオキシ基と、芳香環及びヒドロキシ基の少なくとも一方と、を有する（メタ）アクリルモノマー成分である。モノ（メタ）アクリルモノマー（Ｂ－３）を用いることで、光硬化性組成物の粘度を低下させつつ、試験片Ａ１の２５℃における貯蔵弾性率及び３７℃における貯蔵弾性率を増加させる傾向にある。 ≪Mono(meth)acrylic monomer (B-3)≫
The mono(meth)acrylic monomer (B-3) is a (meth)acrylic monomer component having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group. By using the mono(meth)acrylic monomer (B-3), while decreasing the viscosity of the photocurable composition, there was a tendency to increase the storage modulus at 25 °C and the storage modulus at 37 °C of test piece A1. be.
　モノ（メタ）アクリルモノマー（Ｂ－３）の分子量は、１３０以上３５０以下であることが好ましく、１３０以上３２０以下であることがより好ましく、１３０以上３００以下であることがさらに好ましい。 The molecular weight of the mono(meth)acrylic monomer (B-3) is preferably 130 or more and 350 or less, more preferably 130 or more and 320 or less, and even more preferably 130 or more and 300 or less.
　モノ（メタ）アクリルモノマー（Ｂ－３）の重量平均分子量は、１３０以上３５０以下であることが好ましく、１３０以上３２０以下であることがより好ましく、１３０以上３００以下であることがさらに好ましい。 The weight average molecular weight of the mono(meth)acrylic monomer (B-3) is preferably 130 or more and 350 or less, more preferably 130 or more and 320 or less, and even more preferably 130 or more and 300 or less.
　モノ（メタ）アクリルモノマー（Ｂ－３）は、下記式（３）で表される化合物を含んでいてもよい。 The mono(meth)acrylic monomer (B-3) may contain a compound represented by the following formula (3).
　式（３）中、Ｒ１１は、芳香族構造及びヒドロキシ基の少なくとも一方を有する１価の有機基である。 In formula (3), R 11 is a monovalent organic group having at least one of an aromatic structure and a hydroxy group.
　式（３）中のＲ１１における芳香族構造を有する１価の有機基は、炭素数２～３０の１価の有機基であることが好ましく、炭素数３～２０の１価の有機基であることがより好ましい。 The monovalent organic group having an aromatic structure in R 11 in formula (3) is preferably a monovalent organic group having 2 to 30 carbon atoms, and preferably a monovalent organic group having 3 to 20 carbon atoms. It is more preferable that there be.
　式（３）中、Ｒ１１は、下記式（４）で表される有機基であってもよい。 In formula (3), R 11 may be an organic group represented by formula (4) below.
　式（４）中、Ｌ１は、単結合又は炭素数１～３０のＯ又はＮであるヘテロ原子を有していてもよい２価の鎖状炭化水素基であり、Ａは、炭素数２～１０のヒドロキシアルキル基又は炭素数６～３０のアリール基である。＊は結合位置を表す。 In formula (4), L 1 is a divalent chain hydrocarbon group which may have a single bond or a heteroatom which is O or N having 1 to 30 carbon atoms, and A is a divalent chain hydrocarbon group having 2 to 30 carbon atoms. ~10 hydroxyalkyl group or an aryl group having 6 to 30 carbon atoms. * represents the bonding position.
　式（４）中、Ｌ１で表される炭素数１～３０のＯ又はＮであるヘテロ原子を有していてもよい２価の鎖状炭化水素基は、直鎖状であっても分岐鎖状であってもよい。
　Ｌ１で表される炭素数１～３０のＯ又はＮであるヘテロ原子を有していてもよい２価の鎖状炭化水素基の炭素数は、１～２０であることがより好ましく、１～１０であることがさらに好ましく、１～８であることが特に好ましい。
　Ｌ１で表される２価の鎖状炭化水素基がヘテロ原子を含む場合、Ｌ１中のヘテロ原子の数は１～３であることが好ましく、１又は２であることがさらに好ましい。 In formula (4), the divalent chain hydrocarbon group represented by L 1 which may have a hetero atom of O or N having 1 to 30 carbon atoms may be linear or branched. It may be chain-like.
The carbon number of the divalent chain hydrocarbon group optionally having a hetero atom of O or N having 1 to 30 carbon atoms, represented by L 1 , is more preferably 1 to 20, and 1 to 30 carbon atoms. It is more preferably from 1 to 10, and particularly preferably from 1 to 8.
When the divalent chain hydrocarbon group represented by L 1 contains a heteroatom, the number of heteroatoms in L 1 is preferably 1 to 3, more preferably 1 or 2.
　Ｌ１で表される上記２価の鎖状炭化水素基は、置換基を有していてもよい。
　置換基の好適な例としては、炭素数１～３のアルキル基、ヒドロキシ基、水素原子のうち１又は２がヒドロキシ基で置換された炭素数１～３のアルキル基が挙げられる。
　Ｌ１で表される上記２価の鎖状炭化水素基は、ウレタン結合を含んでいてもよい。Ｌ１で表される上記２価の鎖状炭化水素基がウレタン結合を含む場合、Ｌ１中のウレタン結合の数は、１又は２であってよい。 The divalent chain hydrocarbon group represented by L 1 may have a substituent.
Suitable examples of the substituent include an alkyl group having 1 to 3 carbon atoms, a hydroxy group, and an alkyl group having 1 to 3 carbon atoms in which one or two of the hydrogen atoms are substituted with a hydroxy group.
The divalent chain hydrocarbon group represented by L 1 may include a urethane bond. When the divalent chain hydrocarbon group represented by L 1 contains a urethane bond, the number of urethane bonds in L 1 may be 1 or 2.
　式（４）中のＬ１で表される上記２価の鎖状炭化水素基の具体例としては、例えば、以下の基が挙げられる。以下の基において、＊は結合位置を表す。
Specific examples of the divalent chain hydrocarbon group represented by L 1 in formula (4) include the following groups. In the following groups, * represents the bonding position.
　式（４）中、Ａが炭素数２～１０のヒドロキシアルキル基である場合、Ｌ１は、単結合であることが好ましい。このとき、モノ（メタ）アクリルモノマー（Ｂ－３）は、４－ヒドロキシブチル（メタ）アクリレート及び２－ヒドロキシプロピル（メタ）アクリレートが好ましい。 In formula (4), when A is a hydroxyalkyl group having 2 to 10 carbon atoms, L 1 is preferably a single bond. At this time, the mono(meth)acrylic monomer (B-3) is preferably 4-hydroxybutyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.
　式（４）中、Ａで表される炭素数６～３０のアリール基における芳香族構造としては、例えば、フェニル構造、ビフェニル構造、ナフチル構造、アントリル構造が挙げられる。 In formula (4), the aromatic structure in the aryl group having 6 to 30 carbon atoms represented by A includes, for example, a phenyl structure, a biphenyl structure, a naphthyl structure, and an anthryl structure.
　式（４）中のＡで表される基は、置換基を有していてもよい。
　上記置換基の好適な例としては、
メチル基、エチル基などの炭素数１～６のアルキル基；
ヒドロキシ基；
１つ又は２つのヒドロキシ基で置換された炭素数１～６のアルキル基；
アリール基；
シクロペンチル基、シクロヘキシル基などの炭素数３～６のシクロアルキル基；
トリル基；
キシリル基；
クミル基；
スチリル基；
メトキシフェニル基、エトキシフェニル基、プロポキシフェニル基などのアルコキシフェニル基；
フェノキシメチル基、フェノキシエチル基、フェノキシプロピル基などのフェノキシアルキル基等が挙げられる。 The group represented by A in formula (4) may have a substituent.
Suitable examples of the above substituents include:
an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group;
Hydroxy group;
an alkyl group having 1 to 6 carbon atoms substituted with one or two hydroxy groups;
Aryl group;
Cycloalkyl groups having 3 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group;
tolyl group;
xylyl group;
Cumyl group;
Styryl group;
Alkoxyphenyl groups such as methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group;
Examples include phenoxyalkyl groups such as phenoxymethyl group, phenoxyethyl group, and phenoxypropyl group.
　式（４）中のＡで表される基としては、例えば、以下の例を挙げることができる。＊は結合位置を表す。 Examples of the group represented by A in formula (4) include the following examples. * represents the bonding position.
　（メタ）アクリルモノマー（Ｂ）の含有量は、前記（メタ）アクリルモノマー成分の全量に対し、３質量％～８０質量％であることが好ましく、１０質量％～７０質量％であることがより好ましく、２０質量％～６０質量％であることがさらに好ましい。 The content of the (meth)acrylic monomer (B) is preferably 3% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, based on the total amount of the (meth)acrylic monomer component. The content is preferably 20% by mass to 60% by mass, more preferably 20% by mass to 60% by mass.
　ジ（メタ）アクリルモノマー（Ａ）及び（メタ）アクリルモノマー（Ｂ）の合計含有量は、本開示の光硬化性組成物に含まれる（メタ）アクリルモノマー成分の全量に対し、８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることがさらに好ましい。
　ジ（メタ）アクリルモノマー（Ａ）及び（メタ）アクリルモノマー（Ｂ）の合計含有量の上限は特に限定されず、１００質量％以下であればよい。 The total content of the di(meth)acrylic monomer (A) and the (meth)acrylic monomer (B) is 80% by mass or more based on the total amount of the (meth)acrylic monomer component contained in the photocurable composition of the present disclosure. The content is preferably 90% by mass or more, and even more preferably 95% by mass or more.
The upper limit of the total content of di(meth)acrylic monomer (A) and (meth)acrylic monomer (B) is not particularly limited, and may be 100% by mass or less.
　本開示の光硬化性組成物では、（メタ）アクリルモノマー成分のメタクリル基とアクリル基のうち、アクリル基の含有量を向上させることで（例えば、光硬化性組成物中のアクリルモノマーの含有量を高くすることで）、試験片Ａ１の２５℃における貯蔵弾性率を３７℃における貯蔵弾性率よりも優先的に向上させることができる。また、（メタ）アクリルモノマー成分のメタクリル基とアクリル基のうち、メタクリル基の含有量を向上させることで（例えば、光硬化性組成物中のメタクリルモノマーの含有量を高くすることで）、試験片Ａ１の３７℃における貯蔵弾性率を２５℃における貯蔵弾性率よりも優先的に向上させることができる。
　また、（メタ）アクリルモノマー成分のメタクリル基とアクリル基のうち、アクリル基の含有量を減少させることで（例えば、光硬化性組成物中のアクリルモノマーの含有量を低くすることで）、試験片Ａ１の２５℃における貯蔵弾性率を３７℃における貯蔵弾性率よりも優先的に減少させることができ、また、（メタ）アクリルモノマー成分のメタクリル基とアクリル基のうち、メタクリル基の含有量を減少させることで（例えば、光硬化性組成物中のメタクリルモノマーの含有量を低くすることで）、試験片Ａ１の３７℃における貯蔵弾性率を２５℃における貯蔵弾性率よりも優先的に減少させることができる。 In the photocurable composition of the present disclosure, by increasing the content of acrylic groups among the methacrylic groups and acrylic groups of the (meth)acrylic monomer component (for example, increasing the content of the acrylic monomer in the photocurable composition). ), it is possible to improve the storage modulus of the test piece A1 at 25°C more preferentially than the storage modulus at 37°C. In addition, by increasing the content of methacrylic groups among the methacrylic groups and acrylic groups of the (meth)acrylic monomer component (for example, by increasing the content of methacrylic monomer in the photocurable composition), the test The storage modulus of piece A1 at 37°C can be improved more preferentially than the storage modulus at 25°C.
In addition, by reducing the content of the acrylic group among the methacrylic group and the acrylic group of the (meth)acrylic monomer component (for example, by lowering the content of the acrylic monomer in the photocurable composition), the test The storage modulus at 25°C of piece A1 can be reduced more preferentially than the storage modulus at 37°C, and the content of methacrylic groups among the methacrylic groups and acrylic groups of the (meth)acrylic monomer component can be reduced. By decreasing (e.g., by lowering the content of methacrylic monomer in the photocurable composition), the storage modulus of test piece A1 at 37°C is preferentially reduced over the storage modulus at 25°C. be able to.
［光重合開始剤］
　本開示の光硬化性組成物は、光重合開始剤を含む。
　本開示の光硬化性組成物は、光重合開始剤を１種のみ含有していてもよいし、２種以上含有していてもよい。 [Photopolymerization initiator]
The photocurable composition of the present disclosure includes a photopolymerization initiator.
The photocurable composition of the present disclosure may contain only one kind of photopolymerization initiator, or may contain two or more kinds of photopolymerization initiators.
　光重合開始剤は、光を照射することでラジカルを発生するものであれば特に限定されず、光造形の際に用いる光の波長でラジカルを発生するものであることが好ましい。
　光造形の際に用いる光の波長としては、一般的には３６５ｎｍ～５００ｎｍが挙げられるが、実用上好ましくは３６５ｎｍ～４３０ｎｍであり、より好ましくは３６５ｎｍ～４２０ｎｍである。 The photopolymerization initiator is not particularly limited as long as it generates radicals when irradiated with light, and is preferably one that generates radicals at the wavelength of light used during stereolithography.
The wavelength of the light used during stereolithography is generally 365 nm to 500 nm, but is practically preferably 365 nm to 430 nm, and more preferably 365 nm to 420 nm.
　光重合開始剤としては、例えば、アシルフォスフィンオキサイド系化合物、ベンゾイルぎ酸アルキル化合物、アルキルフェノン系化合物、チタノセン系化合物、オキシムエステル系化合物、ベンゾイン系化合物、アセトフェノン系化合物、ベンゾフェノン系化合物、チオキサントン系化合物、α－アシロキシムエステル系化合物、フェニルグリオキシレート系化合物、ベンジル系化合物、アゾ系化合物、ジフェニルスルフィド系化合物、有機色素系化合物、鉄－フタロシアニン系化合物、ベンゾインエーテル系化合物、アントラキノン系化合物等が挙げられる。 Examples of photopolymerization initiators include acylphosphine oxide compounds, alkyl benzoylformates, alkylphenone compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, and thioxanthone compounds. compounds, α-acyloxime ester compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, anthraquinone compounds, etc. can be mentioned.
　アシルフォスフィンオキサイド系化合物としては、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、２，６－ジメトキシベンゾイルジフェニルフォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等が挙げられる。 Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. can be mentioned.
　本開示の光硬化性組成物中における光重合開始剤の合計含有量は、光硬化性組成物の全量に対し、０．１質量％～５質量％であることが好ましく、０．５質量％～４質量％であることがより好ましく、０．５質量％～３質量％であることがさらに好ましい。 The total content of the photopolymerization initiator in the photocurable composition of the present disclosure is preferably 0.1% by mass to 5% by mass, and 0.5% by mass based on the total amount of the photocurable composition. It is more preferably 4% by mass, and even more preferably 0.5% by mass to 3% by mass.
　光重合開始剤がアシルフォスフィンオキサイド系化合物を含む場合、アシルフォスフィンオキサイド系化合物の含有量は、光重合開始剤の全量に対し、５０質量％～１００質量％であってもよく、７０質量％～１００質量％であってもよく、９０質量％～１００質量％であってもよい。 When the photopolymerization initiator contains an acylphosphine oxide compound, the content of the acylphosphine oxide compound may be 50% by mass to 100% by mass, and 70% by mass based on the total amount of the photopolymerization initiator. % to 100% by mass, or 90% to 100% by mass.
　前述の（ａ）又は（ｂ）を満たす場合、２種類以上のジ（メタ）アクリルモノマー（Ａ）及び光重合開始剤の合計含有量、又は、ジ（メタ）アクリルモノマー（Ａ）、（メタ）アクリルモノマー（Ｂ）及び光重合開始剤の合計含有量は、本開示の光硬化性組成物の全量に対し、それぞれ独立に、８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることがさらに好ましい。
　２種類以上のジ（メタ）アクリルモノマー（Ａ）及び光重合開始剤の合計含有量の上限、又は、ジ（メタ）アクリルモノマー（Ａ）、（メタ）アクリルモノマー（Ｂ）及び光重合開始剤の合計含有量の上限は特に限定されず、１００質量％以下であればよい。 When the above (a) or (b) is satisfied, the total content of two or more di(meth)acrylic monomers (A) and a photopolymerization initiator, or the total content of di(meth)acrylic monomers (A), (meth) ) The total content of the acrylic monomer (B) and the photopolymerization initiator is preferably 80% by mass or more, and preferably 90% by mass or more, each independently of the total amount of the photocurable composition of the present disclosure. It is more preferable that the amount is 95% by mass or more.
The upper limit of the total content of two or more types of di(meth)acrylic monomers (A) and photopolymerization initiator, or di(meth)acrylic monomer (A), (meth)acrylic monomer (B), and photopolymerization initiator The upper limit of the total content of is not particularly limited, and may be 100% by mass or less.
＜その他の成分＞
　本開示の光硬化性組成物は、必要に応じて、上述した成分以外のその他の成分を１種類以上含有していてもよい。
　光硬化性組成物が、その他の成分を含む場合、（メタ）アクリルモノマー成分及び光重合開始剤の合計質量は、光硬化性組成物の全量に対し、３０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、７０質量％以上であることがさらに好ましく、８０質量％以上であることがさらに好ましく、９０質量％以上であることがさらに好ましい。 <Other ingredients>
The photocurable composition of the present disclosure may contain one or more types of components other than the above-mentioned components, if necessary.
When the photocurable composition contains other components, the total mass of the (meth)acrylic monomer component and the photopolymerization initiator is preferably 30% by mass or more based on the total amount of the photocurable composition, It is more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more.
　その他の成分としては、例えば、色材、シランカップリング剤（例えば３－アクリロキシプロピルトリメトキシシラン）等のカップリング剤、ゴム剤、イオントラップ剤、イオン交換剤、レベリング剤、可塑剤、消泡剤等の添加剤、熱重合開始剤等も挙げられる。
　本開示の光硬化性組成物が熱重合開始剤を含む場合には、光硬化と熱硬化との併用が可能となる。熱重合開始剤としては、例えば、熱ラジカル発生剤、アミン化合物などが挙げられる。 Other ingredients include, for example, colorants, coupling agents such as silane coupling agents (for example, 3-acryloxypropyltrimethoxysilane), rubber agents, ion trapping agents, ion exchange agents, leveling agents, plasticizers, and erasers. Additives such as foaming agents, thermal polymerization initiators, etc. may also be mentioned.
When the photocurable composition of the present disclosure contains a thermal polymerization initiator, photocuring and thermal curing can be used together. Examples of the thermal polymerization initiator include thermal radical generators and amine compounds.
　その他の成分としては、無機フィラーも挙げられる。
　しかし、硬化物の造形精度をより向上させる観点から、本開示の光硬化性組成物は、無機フィラー（例えば、シリカ、バリウムボロシリケートガラス、等。以下同じ。）を含有しないか、又は、無機フィラーを含む場合には、光硬化性組成物の全量に対する無機フィラーの含有量が６０質量％以下（より好ましくは４０質量％以下、さらに好ましくは２０質量％以下、特に好ましくは１０質量％以下）であることが好ましい。 Other components include inorganic fillers.
However, from the viewpoint of further improving the modeling precision of the cured product, the photocurable composition of the present disclosure does not contain an inorganic filler (for example, silica, barium borosilicate glass, etc.; the same applies hereinafter), or When a filler is included, the content of the inorganic filler is 60% by mass or less (more preferably 40% by mass or less, still more preferably 20% by mass or less, particularly preferably 10% by mass or less) based on the total amount of the photocurable composition. It is preferable that
　本開示の光硬化性組成物の調製方法は特に制限されない。
　本開示の光硬化性組成物の調製方法としては、例えば、（メタ）アクリルモノマー成分、光重合開始剤及び必要に応じてその他の成分を混合する方法が挙げられる。
　各成分を混合する手段は特に限定されず、例えば、超音波による溶解、双腕式撹拌機、ロール混練機、２軸押出機、ボールミル混練機、及び遊星式撹拌機等の手段が含まれる。
　本実施形態の光硬化性組成物は、各成分を混合した後、フィルタでろ過して不純物を取り除き、さらに真空脱泡処理を施すことによって調製してもよい。 The method for preparing the photocurable composition of the present disclosure is not particularly limited.
Examples of the method for preparing the photocurable composition of the present disclosure include a method of mixing a (meth)acrylic monomer component, a photopolymerization initiator, and other components as necessary.
The means for mixing each component is not particularly limited, and includes means such as ultrasonic dissolution, a double-arm stirrer, a roll kneader, a twin-screw extruder, a ball mill kneader, and a planetary stirrer.
The photocurable composition of this embodiment may be prepared by mixing each component, filtering the mixture through a filter to remove impurities, and further performing a vacuum defoaming treatment.
＜光硬化性組成物の好ましい粘度＞
　本開示の光硬化性組成物は、Ｅ型粘度計により２５℃及び５０ｒｐｍの条件で測定される粘度（以下、単に「粘度」ともいう）が、５ｍＰａ・ｓ～６０００ｍＰａ・ｓであることが好ましい。
　ここで、ｒｐｍは、revolutions per minute（回転毎分）を意味する。
　粘度が５ｍＰａ・ｓ～６０００ｍＰａ・ｓである場合には、硬化物（特に、光造形物）を製造する際の光硬化性組成物の取り扱い性に優れる。
　粘度は、１０ｍＰａ・ｓ～５０００ｍＰａ・ｓであることがより好ましく、２０ｍＰａ・ｓ～５０００ｍＰａ・ｓであることがさらに好ましく、１００ｍＰａ・ｓ～４５００ｍＰａ・ｓであることがさらに好ましい。 <Preferred viscosity of photocurable composition>
The photocurable composition of the present disclosure preferably has a viscosity (hereinafter also simply referred to as "viscosity") measured by an E-type viscometer at 25° C. and 50 rpm of 5 mPa·s to 6000 mPa·s. .
Here, rpm means revolutions per minute.
When the viscosity is from 5 mPa·s to 6000 mPa·s, the photocurable composition has excellent handling properties when producing a cured product (particularly a stereolithographic product).
The viscosity is more preferably 10 mPa·s to 5000 mPa·s, even more preferably 20 mPa·s to 5000 mPa·s, even more preferably 100 mPa·s to 4500 mPa·s.
　以下、第２実施形態の光硬化性組成物について説明する。なお、前述の第１実施形態の光硬化性組成物と共通する事項については、その説明を省略する。 Hereinafter, the photocurable composition of the second embodiment will be explained. Note that descriptions of items common to the photocurable composition of the first embodiment described above will be omitted.
［第２実施形態］
〔光硬化性組成物〕
　本開示の第２実施形態の光硬化性組成物は、（メタ）アクリルモノマー成分と、光重合開始剤と、を含む光硬化性組成物であって、前記（メタ）アクリルモノマー成分が、
　１つの（メタ）アクリロイルオキシ基と、芳香環と、を有するモノ（メタ）アクリルモノマー（Ｘ）と、環構造又はウレタン結合の少なくともいずれか一方と、２つの（メタ）アクリロイルオキシ基と、を有し、シロキサン結合を有さないジ（メタ）アクリルモノマー（Ｙ）と、シロキサン結合と、２つ以上の（メタ）アクリロイルオキシ基と、を有する多官能（メタ）アクリルモノマー（Ｚ）と、を含む。 [Second embodiment]
[Photocurable composition]
The photocurable composition of the second embodiment of the present disclosure is a photocurable composition containing a (meth)acrylic monomer component and a photopolymerization initiator, wherein the (meth)acrylic monomer component is
A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring, at least one of a ring structure or a urethane bond, and two (meth)acryloyloxy groups, a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups; including.
　本開示の光硬化性組成物は、（メタ）アクリルモノマー成分と、光重合開始剤と、を含み、（メタ）アクリルモノマー成分が、モノ（メタ）アクリルモノマー（Ｘ）と、ジ（メタ）アクリルモノマー（Ｙ）と、多官能（メタ）アクリルモノマー（Ｚ）と、を含む。このような光硬化性組成物を用いることで、有床義歯の製造時における変形が抑制された鋳型又は鋳型を用いて有床義歯を製造する際に、鋳型内から有床義歯を取り出しやすい鋳型の作製が可能となる。 The photocurable composition of the present disclosure includes a (meth)acrylic monomer component and a photopolymerization initiator, and the (meth)acrylic monomer component includes a mono(meth)acrylic monomer (X) and a di(meth)acrylic monomer (X). It includes an acrylic monomer (Y) and a polyfunctional (meth)acrylic monomer (Z). By using such a photocurable composition, deformation during the production of dentures can be suppressed, or when manufacturing dentures using a mold, the dentures can be easily removed from the mold. It becomes possible to create
　本開示の光硬化性組成物に対し波長４０５ｎｍの可視光を照射量１１ｍＪ／ｃｍ２にて照射して厚み５０μｍの硬化層Ａ１を形成し、前記硬化層Ａ１を厚み方向に積層させることにより、長さ４０ｍｍ、幅１０ｍｍ、厚み１．０ｍｍの矩形板形状の造形物Ａ１を形成し、前記造形物Ａ１に対し、波長３６５ｎｍの紫外線を照射量３Ｊ／ｃｍ２にて照射する条件の光造形により、長さ４０ｍｍ、幅１０ｍｍ、厚み１．０ｍｍの矩形板形状の試験片Ａ１を作製した場合に、
　前記試験片Ａ１の２５℃における貯蔵弾性率が、鋳型の変形を抑制する観点（例えば、本開示の光硬化性組成物を用いて作製した鋳型に義歯床作製用等の光硬化性組成物を注入して重合する際の鋳型の変形を抑制する観点）から、１０ＭＰａ以上であってもよく、鋳型からの抜き出し性の観点（例えば、有床義歯を鋳型から抜き出す際の鋳型、有床義歯等の損傷を抑制する観点）から、１００ＭＰａ以下であってもよい。
　前記試験片Ａ１の３７℃における貯蔵弾性率が、鋳型からの抜き出し性の観点から、４００ＭＰａ以下であってもよく、使用時の鋳型の変形を抑制する観点から、６ＭＰａ以上であってもよい。
　２５℃における貯蔵弾性率及び３７℃における貯蔵弾性率が上記の数値範囲を満たす光硬化性組成物を用いることで、有床義歯の製造時における変形が抑制された鋳型又は鋳型を用いて有床義歯を製造する際に、鋳型内から有床義歯を取り出しやすい鋳型をより好適に作製することが可能である。 By irradiating the photocurable composition of the present disclosure with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer A1 having a thickness of 50 μm, and laminating the cured layer A1 in the thickness direction, A rectangular plate-shaped object A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 3 J/cm 2 by stereolithography. , When a rectangular plate-shaped test piece A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was prepared,
The storage modulus of the test piece A1 at 25° C. is determined from the viewpoint of suppressing deformation of the mold (for example, applying a photocurable composition for making a denture base to a mold prepared using the photocurable composition of the present disclosure). From the viewpoint of suppressing deformation of the mold during injection and polymerization), the pressure may be 10 MPa or more, and from the viewpoint of ease of extraction from the mold (for example, from the viewpoint of removing the denture from the mold, the mold when removing the denture from the mold, the denture, etc.) 100 MPa or less may be sufficient from the viewpoint of suppressing damage to
The storage modulus of the test piece A1 at 37° C. may be 400 MPa or less from the viewpoint of ease of extraction from the mold, and may be 6 MPa or more from the viewpoint of suppressing mold deformation during use.
By using a photocurable composition whose storage modulus at 25°C and storage modulus at 37°C satisfies the above numerical ranges, deformation during the production of dentures with dentures is suppressed or using a mold. When manufacturing a denture, it is possible to more suitably create a mold from which the denture can be easily removed from the mold.
　第２実施形態の光硬化性組成物では、前記試験片Ａ１の２５℃における貯蔵弾性率は、１０ＭＰａ未満であってもよく、例えば、１ＭＰａ～１０ＭＰａであってもよく、２ＭＰａ～８ＭＰａであってもよい。 In the photocurable composition of the second embodiment, the storage modulus of the test piece A1 at 25°C may be less than 10 MPa, for example, 1 MPa to 10 MPa, or 2 MPa to 8 MPa. Good too.
　第２実施形態の光硬化性組成物では、前記試験片Ａ１の３７℃における貯蔵弾性率は、例えば、０．５ＭＰａ～２０ＭＰａであってもよく、１ＭＰａ～１０ＭＰａであってもよく、１ＭＰａ～６ＭＰａであってもよい。 In the photocurable composition of the second embodiment, the storage modulus of the test piece A1 at 37° C. may be, for example, 0.5 MPa to 20 MPa, 1 MPa to 10 MPa, or 1 MPa to 6 MPa. It may be.
　第２実施形態の光硬化性組成物の硬化物を鋳型として用いる場合、その鋳型を用いて製造された部材（例えば、有床義歯）の鋳型に対する離型性が向上し、かつ、離型時における靭性が向上して硬化物が破断しにくくなる。 When the cured product of the photocurable composition of the second embodiment is used as a mold, the releasability of a member manufactured using the mold (for example, a denture) from the mold is improved, and when the mold is released, The toughness of the cured product is improved and the cured product is less likely to break.
　（メタ）アクリルモノマー成分は、１つの（メタ）アクリロイルオキシ基と、芳香環と、を有するモノ（メタ）アクリルモノマー（Ｘ）を含む。モノ（メタ）アクリルモノマー（Ｘ）を用いることで、（メタ）アクリルモノマー成分中の芳香環濃度が高まり、鋳型内から有床義歯を取り出しやすくなる（離型性が高まる）傾向にあり、鋳型内から有床義歯を取り出す際の破断を抑制できる（靱性に優れる）傾向にある。さらに、有床義歯の製造時における変形が抑制された鋳型を好適に作製でき、単官能モノマーを使用することで鋳型の柔軟性を高められるため、鋳型の形状回復性も向上させることができる。また、モノ（メタ）アクリルモノマー（Ｘ）は、光硬化性組成物の硬化物の２５℃における貯蔵弾性率、３７℃における貯蔵弾性率を低く調整する際に好適に用いられる。 The (meth)acrylic monomer component includes a mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring. By using the mono(meth)acrylic monomer (X), the concentration of aromatic rings in the (meth)acrylic monomer component increases, which tends to make it easier to remove the denture from the mold (improving mold releasability). It tends to prevent breakage when the denture is taken out from inside (it has excellent toughness). Furthermore, it is possible to suitably create a mold that suppresses deformation during the production of dentures, and by using a monofunctional monomer, the flexibility of the mold can be increased, so the shape recovery of the mold can also be improved. Furthermore, the mono(meth)acrylic monomer (X) is suitably used when adjusting the storage modulus at 25° C. and the storage modulus at 37° C. of the cured product of the photocurable composition to be low.
　モノ（メタ）アクリルモノマー（Ｘ）の分子量は、１６０～４００であってもよく、１８０～３００であってもよい。 The molecular weight of the mono(meth)acrylic monomer (X) may be from 160 to 400, or from 180 to 300.
　モノ（メタ）アクリルモノマー（Ｘ）の重量平均分子量は、１６０～４００であってもよく、１８０～３００であってもよい。 The weight average molecular weight of the mono(meth)acrylic monomer (X) may be from 160 to 400, or from 180 to 300.
　分子量の異なる２種のモノ（メタ）アクリルモノマー（Ｘ）を併用してもよい。これにより、重合体中のモノ（メタ）アクリルモノマー（Ｘ）の分散性が増して形状回復速度が向上する傾向にある。 Two types of mono(meth)acrylic monomers (X) having different molecular weights may be used together. This tends to increase the dispersibility of the mono(meth)acrylic monomer (X) in the polymer and improve the shape recovery speed.
　モノ（メタ）アクリルモノマー（Ｘ）は、１つの（メタ）アクリロイルオキシ基と、芳香環と、を有する化合物であれば特に限定されず、例えば、以下の式（５）で表される化合物であってもよい。 The mono(meth)acrylic monomer (X) is not particularly limited as long as it is a compound having one (meth)acryloyloxy group and an aromatic ring, and for example, a compound represented by the following formula (5). There may be.
　式（５）中、Ｒ１は２価の連結基であり、Ｒ２は置換基を有していてもよいアルキル基又はアリール基であり、Ｒ３は水素原子又はメチル基であり、ｎは０～５の整数である。 In formula (5), R 1 is a divalent linking group, R 2 is an alkyl group or aryl group that may have a substituent, R 3 is a hydrogen atom or a methyl group, and n is It is an integer from 0 to 5.
　式（５）中、Ｒ１はアルキレン基、アリーレン基（フェニレン基等）、アルキレンアリーレン基（アルキレンフェニレン基等）、アリーレンアルキレン基（フェニレンアルキレン基、アルキレンオキシ基、アリーレンオキシ基又はこれらの２つ以上の組み合わせであってもよい。また、Ｒ１に含まれる水素原子は、ヒドロキシ基、アルキル基、アリール基、アミノ基等に置換されていてもよい。
　式（５）中、Ｒ１の主鎖の原子数は、１～２０であってもよく、２～１０であってもよい。Ｒ１の炭素数は、１～２０であってもよく、２～１０であってもよい。 In formula (5), R 1 is an alkylene group, an arylene group (phenylene group, etc.), an alkylene arylene group (alkylene phenylene group, etc.), an arylene alkylene group (phenylene alkylene group, alkyleneoxy group, aryleneoxy group, or two thereof) A combination of the above may be used.Furthermore, the hydrogen atom contained in R1 may be substituted with a hydroxy group, an alkyl group, an aryl group, an amino group, or the like.
In formula (5), the number of atoms in the main chain of R 1 may be from 1 to 20, or from 2 to 10. The number of carbon atoms in R 1 may be from 1 to 20, or from 2 to 10.
　式（５）中、ｎは０又は１であることが好ましい。ｎが１～５の場合、Ｒ２は置換基を有していてもよいフェニル基であることが好ましい。Ｒ２の炭素数は、１～２０であってもよく、１～１０であってもよい。Ｒ２におけるアルキル基又はアリール基が有してもよい置換基としては、ヒドロキシ基、アルキル基、アリール基、アミノ基等が挙げられる。 In formula (5), n is preferably 0 or 1. When n is 1 to 5, R 2 is preferably a phenyl group which may have a substituent. The number of carbon atoms in R 2 may be from 1 to 20, or from 1 to 10. Examples of substituents that the alkyl group or aryl group in R 2 may have include a hydroxy group, an alkyl group, an aryl group, and an amino group.
　（メタ）アクリルモノマー成分は、環構造又はウレタン結合の少なくともいずれか一方と、２つの（メタ）アクリロイルオキシ基と、を有し、シロキサン結合を有さないジ（メタ）アクリルモノマー（Ｙ）を含む。環構造を有するジ（メタ）アクリルモノマー（Ｙ）は、有床義歯の製造時における鋳型の変形抑制、及び鋳型の耐水性向上に好適に寄与する。また、環構造が芳香環を含む場合、（メタ）アクリルモノマー成分中の芳香環濃度が高まり、離型性が高まり、かつ靱性に優れる傾向にある。ウレタン結合を有するジ（メタ）アクリルモノマー（Ｙ）は、鋳型内から有床義歯を取り出す際の破断を抑制でき、靱性に優れる傾向にある。また、ジ（メタ）アクリルモノマー（Ｙ）は、光硬化性組成物の硬化物の２５℃における貯蔵弾性率、３７℃における貯蔵弾性率を高く調整する際に好適に用いられる。 The (meth)acrylic monomer component is a di(meth)acrylic monomer (Y) that has at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and does not have a siloxane bond. include. The di(meth)acrylic monomer (Y) having a ring structure suitably contributes to suppressing deformation of a mold during the production of a denture and improving the water resistance of the mold. Further, when the ring structure includes an aromatic ring, the concentration of the aromatic ring in the (meth)acrylic monomer component tends to increase, the mold releasability increases, and the toughness tends to be excellent. The di(meth)acrylic monomer (Y) having a urethane bond can suppress breakage when the denture is taken out from the mold, and tends to have excellent toughness. Further, the di(meth)acrylic monomer (Y) is suitably used when adjusting the storage modulus at 25° C. and the storage modulus at 37° C. of the cured product of the photocurable composition to be high.
　ジ（メタ）アクリルモノマー（Ｙ）は、環構造又はウレタン結合の少なくともいずれか一方と、２つの（メタ）アクリロイルオキシ基と、を有し、シロキサン結合を有さない化合物であれば特に限定されない。環構造としては、芳香環構造又は脂環式構造が挙げられる。 The di(meth)acrylic monomer (Y) is not particularly limited as long as it is a compound that has at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and does not have a siloxane bond. . Examples of the ring structure include an aromatic ring structure and an alicyclic structure.
　ジ（メタ）アクリルモノマー（Ｙ）は、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離は、１０Å以上２００Å以下であってもよい。前述の酸素原子間の距離は、１０Å以上２５Å未満であってもよく、２５Å以上８０Å以下であってもよく、８０Å超２００Å未満であってもよい。例えば、前述の酸素原子間の距離を小さくすることで、鋳型の弾性率を高めて有床義歯の製造時における鋳型の変形を好適に抑制できる傾向にあり、前述の酸素原子間の距離を長くすることで離型性を高めることができる傾向にある。 The di(meth)acrylic monomer (Y) has an oxygen atom forming an oxy group in one (meth)acryloyloxy group and an oxygen atom forming an oxy group in the other (meth)acryloyloxy group. The distance between them may be 10 Å or more and 200 Å or less. The distance between the aforementioned oxygen atoms may be 10 Å or more and less than 25 Å, 25 Å or more and 80 Å or less, or more than 80 Å and less than 200 Å. For example, by reducing the distance between the oxygen atoms mentioned above, the elastic modulus of the mold can be increased and the deformation of the mold during the manufacture of dentures can be suppressed. This tends to improve mold releasability.
　ジ（メタ）アクリルモノマー（Ｙ）の分子量は、４００～５０００であってもよい。
　ジ（メタ）アクリルモノマー（Ｙ）の重量平均分子量は、４００～４０００であってもよい。 The molecular weight of the di(meth)acrylic monomer (Y) may be 400 to 5,000.
The weight average molecular weight of the di(meth)acrylic monomer (Y) may be from 400 to 4,000.
　分子量の異なる２種のジ（メタ）アクリルモノマー（Ｙ）を併用してもよい。これにより、重合体中のジ（メタ）アクリルモノマー（Ｙ）の分散性が増して形状回復速度が向上する傾向にある。 Two types of di(meth)acrylic monomers (Y) with different molecular weights may be used together. This tends to increase the dispersibility of the di(meth)acrylic monomer (Y) in the polymer and improve the shape recovery speed.
　ジ（メタ）アクリルモノマー（Ｙ）は、ウレタン結合を含む場合に、以下の式（６－１）で表される化合物であってもよく、環構造を含む場合に、以下の式（６－２）で表される化合物であってもよい。ジ（メタ）アクリルモノマー（Ｙ）は、ウレタン結合及び環構造の両方を含む場合、以下の式（６－１）で表される化合物であってもよい。 The di(meth)acrylic monomer (Y) may be a compound represented by the following formula (6-1) when it contains a urethane bond, and it may be a compound represented by the following formula (6-1) when it contains a ring structure. It may also be a compound represented by 2). When the di(meth)acrylic monomer (Y) contains both a urethane bond and a ring structure, it may be a compound represented by the following formula (6-1).
　式（６－１）中、Ｒ１は、それぞれ独立に置換基を有していてもよいアルキレン基、エステル結合、アルキレンオキシ基又はこれらのうち少なくとも２つ以上の組み合わせであり、Ｒ２は置換基を有していてもよいアルキレン基、２価の環構造、エステル結合、ウレタン結合、アルキレンオキシ基又はこれらのうち少なくとも２つ以上の組み合わせであり、Ｒ３は、それぞれ独立に水素原子又はメチル基である。
　式（６－２）中、Ｒ３は、それぞれ独立に水素原子又はメチル基であり、Ｒ４は、それぞれ独立に置換基を有していてもよいアルキレン基、アルキレンオキシ基又はこれらの組み合わせであり、Ｒ５は、それぞれ独立に酸素原子又はエステル結合（＊１－Ｏ－Ｃ（＝Ｏ）－＊２、＊１はＲ４との結合位置であり、＊２はＲ６との結合位置である）であり、Ｒ６は、環構造を含む２価の連結基である。 In formula (6-1), R 1 is an alkylene group, an ester bond, an alkyleneoxy group, or a combination of at least two of these, each of which may independently have a substituent, and R 2 is a substituted an alkylene group which may have a group, a divalent ring structure, an ester bond, a urethane bond, an alkyleneoxy group, or a combination of at least two of these; R 3 is each independently a hydrogen atom or a methyl It is the basis.
In formula (6-2), R 3 is each independently a hydrogen atom or a methyl group, and R 4 is each independently an optionally substituted alkylene group, alkyleneoxy group, or a combination thereof. R 5 is each independently an oxygen atom or an ester bond (*1-OC(=O)-*2, *1 is the bonding position with R 4 , *2 is the bonding position with R 6 ), and R 6 is a divalent linking group containing a ring structure.
　式（６－１）中、Ｒ１が置換基を有していてもよいアルキレン基であるか、あるいは当該アルキレン基を含む場合、置換基としては、フェニルオキシ基等が挙げられる。
　Ｒ１がアルキレンオキシ基であるか、あるいはアルキレンオキシ基を含む場合、当該アルキレンオキシ基は、エチレンオキシ基、プロピレンオキシ基等であってもよい。また、アルキレンオキシ基を複数含む場合は、複数含まれるアルキレンオキシ基は、ポリエチレンオキシ基、ポリプロピレンオキシ基等であってもよい。
　Ｒ１がエステル結合を有する場合、Ｒ１はε－カプロラクトンに由来する構成単位を含んでいてもよく、ε－カプロラクトンに由来する構成単位を複数含んでいてもよい。また、Ｒ１がエステル結合を有する場合、アルキレン基－Ｏ－ＣＯ－アルキレン基であってもよく、このうち－Ｏ－ＣＯ－アルキレン基が繰り返し構造（例えば、２～１０）であってもよい。
　Ｒ１の炭素数は、１～５０であってもよく、２～２５であってもよい。
　式（６－１）中、Ｒ２が置換基を有していてもよいアルキレン基（直鎖であっても分岐鎖であってもよい）である場合、置換基としては、ヒドロキシ基、アルキル基、アリール基、アミノ基等が挙げられる。
　式（６－１）中、Ｒ２が２価の環構造であるか、２価の環構造を含む場合、環構造としては、芳香環又は脂環が挙げられ、具体的には、フェニレン基、シクロヘキシレン基が挙げられる。また、Ｒ２は、２価の環構造と２価のアルキレン基とにより形成される基（例えば、イソホロン基、メチレンビス（シクロヘキシレン）基）を含んでいてもよい。
　また、Ｒ２は、２つの環構造を含む２価の炭化水素基、２つのウレタン結合及びアルキレンオキシ基を含む２価の連結基（例えば、環構造を含む２価の炭化水素基－ウレタン結合－（ポリ）アルキレンオキシ基－ウレタン結合－環構造を含む２価の炭化水素基）であってもよい。
　Ｒ２の炭素数は、１～２００であってよく、２～１００であってもよい。 In formula (6-1), when R 1 is an alkylene group which may have a substituent or contains the alkylene group, examples of the substituent include a phenyloxy group.
When R 1 is an alkyleneoxy group or contains an alkyleneoxy group, the alkyleneoxy group may be an ethyleneoxy group, a propyleneoxy group, or the like. Further, when a plurality of alkyleneoxy groups are included, the plurality of alkyleneoxy groups may be a polyethyleneoxy group, a polypropyleneoxy group, or the like.
When R 1 has an ester bond, R 1 may contain a structural unit derived from ε-caprolactone, or may contain a plurality of structural units derived from ε-caprolactone. Further, when R 1 has an ester bond, it may be an alkylene group -O-CO-alkylene group, and among these, the -O-CO-alkylene group may have a repeating structure (for example, 2 to 10). .
The number of carbon atoms in R 1 may be from 1 to 50, or from 2 to 25.
In formula (6-1), when R 2 is an alkylene group (which may be linear or branched) that may have a substituent, examples of the substituent include a hydroxy group, an alkyl group, aryl group, amino group, etc.
In formula (6-1), when R 2 is a divalent ring structure or includes a divalent ring structure, examples of the ring structure include an aromatic ring or an alicyclic ring, and specifically, a phenylene group. , cyclohexylene group. Furthermore, R 2 may include a group formed by a divalent ring structure and a divalent alkylene group (eg, an isophorone group, a methylenebis(cyclohexylene) group).
In addition, R 2 is a divalent hydrocarbon group containing two ring structures, two urethane bonds, and a divalent linking group containing an alkyleneoxy group (for example, a divalent hydrocarbon group containing a ring structure - a urethane bond). - (poly)alkyleneoxy group - urethane bond - divalent hydrocarbon group containing a ring structure).
The number of carbon atoms in R 2 may be from 1 to 200, or from 2 to 100.
　式（６－２）中、Ｒ４はアルキレンオキシ基であり、かつＲ５は酸素原子であってもよく、あるいは、Ｒ４はアルキレン基であり、かつＲ５はエステル結合（＊１－Ｏ－Ｃ（＝Ｏ）－＊２、＊１はＲ４との結合位置であり、＊２はＲ６との結合位置である）であってもよい。Ｒ６は、フェニレン基又はビスフェノール骨格（例えば、ビスフェノールＡ骨格又はビスフェノールＦ骨格）であってもよい。
　Ｒ４の炭素数は、１～５０であってもよく、２～３０であってもよい。Ｒ６の炭素数は、１～５０であってもよく、２～２０であってもよい。 In formula (6-2), R 4 is an alkyleneoxy group, and R 5 may be an oxygen atom, or R 4 is an alkylene group, and R 5 is an ester bond (*1-O -C(=O)-*2, *1 is the bonding position with R 4 and *2 is the bonding position with R 6 ). R 6 may be a phenylene group or a bisphenol skeleton (eg, a bisphenol A skeleton or a bisphenol F skeleton).
The number of carbon atoms in R 4 may be from 1 to 50, or from 2 to 30. The number of carbon atoms in R 6 may be from 1 to 50, or from 2 to 20.
　（メタ）アクリルモノマー成分は、シロキサン結合（Ｓｉ－Ｏ－Ｓｉ）と、２つ以上の（メタ）アクリロイルオキシ基と、を有する多官能（メタ）アクリルモノマー（Ｚ）を含む。多官能（メタ）アクリルモノマー（Ｚ）を含むことで、（メタ）アクリルモノマー成分中の芳香環濃度が高まり、鋳型内から有床義歯を取り出しやすくなる（離型性が高まる）傾向にあり、有床義歯製作時の変形性に優れ、寸法精度に優れる傾向にある。また、多官能（メタ）アクリルモノマー（Ｚ）は、光硬化性組成物の硬化物の２５℃における貯蔵弾性率、３７℃における貯蔵弾性率を低く調整する際に好適に用いられる。 The (meth)acrylic monomer component includes a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups. By including the polyfunctional (meth)acrylic monomer (Z), the aromatic ring concentration in the (meth)acrylic monomer component increases, which tends to make it easier to remove the denture from the mold (improving mold releasability), It has excellent deformability when manufacturing dentures, and tends to have excellent dimensional accuracy. Further, the polyfunctional (meth)acrylic monomer (Z) is suitably used when adjusting the storage modulus at 25° C. and the storage modulus at 37° C. of the cured product of the photocurable composition to be low.
　多官能（メタ）アクリルモノマー（Ｚ）は、シロキサン結合（Ｓｉ－Ｏ－Ｓｉ）と、２つ以上の（メタ）アクリロイルオキシ基と、を有する。多官能（メタ）アクリルモノマー（Ｚ）はシロキサン結合（Ｓｉ－Ｏ－Ｓｉ）を複数含んでいてもよく、より詳細には、直鎖状のシロキサン結合、直鎖及び分岐を含む梯子状のシロキサン結合、カゴ型のシロキサン結合等を含んでいてもよい。多官能（メタ）アクリルモノマー（Ｚ）は、２つ又は３つ以上の（メタ）アクリロイルオキシ基を含んでいてもよい。 The polyfunctional (meth)acrylic monomer (Z) has a siloxane bond (Si-O-Si) and two or more (meth)acryloyloxy groups. The polyfunctional (meth)acrylic monomer (Z) may contain a plurality of siloxane bonds (Si-O-Si), and more specifically, a linear siloxane bond, a ladder-like siloxane containing a linear chain and a branch. It may contain bonds, cage-type siloxane bonds, and the like. The polyfunctional (meth)acrylic monomer (Z) may contain two or more (meth)acryloyloxy groups.
　シロキサン結合としては、ジメチルシロキサン結合、メチルフェニルシロキサン結合、ジフェニルシロキサン結合等が挙げられ、ジメチルシロキサン結合が好ましい。 Examples of the siloxane bond include a dimethylsiloxane bond, a methylphenylsiloxane bond, a diphenylsiloxane bond, and the like, with a dimethylsiloxane bond being preferred.
　多官能（メタ）アクリルモノマー（Ｚ）は、シロキサン結合（Ｓｉ－Ｏ－Ｓｉ）と、３つ以上の（メタ）アクリロイルオキシ基とを含む化合物であってもよく、３つ以上の（メタ）アクリロイルオキシ基を含むシルセスキオキサンであってもよい。 The polyfunctional (meth)acrylic monomer (Z) may be a compound containing a siloxane bond (Si-O-Si) and three or more (meth)acryloyloxy groups, and three or more (meth)acryloyloxy groups. It may also be a silsesquioxane containing an acryloyloxy group.
　多官能（メタ）アクリルモノマー（Ｚ）の分子量は、４００～５０００であってもよい。
　多官能（メタ）アクリルモノマー（Ｚ）の重量平均分子量は、４００～４０００であってもよい。 The polyfunctional (meth)acrylic monomer (Z) may have a molecular weight of 400 to 5,000.
The weight average molecular weight of the polyfunctional (meth)acrylic monomer (Z) may be from 400 to 4,000.
　多官能（メタ）アクリルモノマー（Ｚ）は、以下の式（７）で表される化合物であってもよい。 The polyfunctional (meth)acrylic monomer (Z) may be a compound represented by the following formula (7).
　式（７）中、Ｒ１は、それぞれ独立に置換基を有していてもよいアルキレン基であり、Ｒ２は、それぞれ独立に置換基を有していてもよいアルキレン基であり、Ｒ３は、それぞれ独立に水素原子又はメチル基であり、Ｒ４は、それぞれ独立にアルキル基、水素原子又はアリール基であり、ｍは０以上の整数であり、ｎは０以上の整数であり、ｌは０以上の整数である。 In formula (7), R 1 is an alkylene group that may each independently have a substituent, R 2 is an alkylene group that may each independently have a substituent, and R 3 are each independently a hydrogen atom or a methyl group, R4 is each independently an alkyl group, a hydrogen atom, or an aryl group, m is an integer of 0 or more, n is an integer of 0 or more, and l is an integer greater than or equal to 0.
　Ｒ１は、メチレン基、エチレン基又はプロピレン基であることが好ましく、Ｒ２は、メチレン基、エチレン基、プロピレン基又はブチレン基であることがより好ましい。
　Ｒ４は、メチル基又はフェニル基であることが好ましく、メチル基であることがより好ましい。
　ｍは、１～３０であってもよく、２～２０であってもよい。他の（メタ）アクリルモノマー成分との相溶性の観点から、ｍは３０以下であることが好ましく、２０以下であることがより好ましい。
　ｎは、０又は１以上であってもよい。ｎが１以上である場合、ｎは１～３０であってもよく、１～２０であってもよい。
　ｌは、０又は１以上であってもよい。ｌが１以上である場合、ｌは１～３０であってもよく、１～２０であってもよい。 R 1 is preferably a methylene group, ethylene group or propylene group, and R 2 is more preferably a methylene group, ethylene group, propylene group or butylene group.
R 4 is preferably a methyl group or a phenyl group, more preferably a methyl group.
m may be from 1 to 30, or from 2 to 20. From the viewpoint of compatibility with other (meth)acrylic monomer components, m is preferably 30 or less, more preferably 20 or less.
n may be 0 or 1 or more. When n is 1 or more, n may be from 1 to 30, or from 1 to 20.
l may be 0 or 1 or more. When l is 1 or more, l may be from 1 to 30, or from 1 to 20.
　（メタ）アクリルモノマー成分において、モノ（メタ）アクリルモノマー（Ｘ）の含有量は、（メタ）アクリルモノマー成分の全量に対し、３０質量％～９０質量％であることが好ましく、４０質量％～８０質量％であることがより好ましい。 In the (meth)acrylic monomer component, the content of the mono(meth)acrylic monomer (X) is preferably from 30% by mass to 90% by mass, and from 40% by mass to the total amount of the (meth)acrylic monomer component. More preferably, it is 80% by mass.
　（メタ）アクリルモノマー成分において、ジ（メタ）アクリルモノマー（Ｙ）の含有量は、（メタ）アクリルモノマー成分の全量に対し、５質量％～５５質量％であることが好ましく、１０質量％～４０質量％であることがより好ましい。 In the (meth)acrylic monomer component, the content of the di(meth)acrylic monomer (Y) is preferably from 5% by mass to 55% by mass, and from 10% by mass to the total amount of the (meth)acrylic monomer component. More preferably, it is 40% by mass.
　（メタ）アクリルモノマー成分において、多官能（メタ）アクリルモノマー（Ｚ）の含有量は、前記（メタ）アクリルモノマー成分の全量に対し、１質量％～６０質量％であることが好ましく、５質量％～５０質量％であることがより好ましい。 In the (meth)acrylic monomer component, the content of the polyfunctional (meth)acrylic monomer (Z) is preferably 1% by mass to 60% by mass, and 5% by mass based on the total amount of the (meth)acrylic monomer component. % to 50% by mass is more preferable.
　（メタ）アクリルモノマー成分において、モノ（メタ）アクリルモノマー（Ｘ）、ジ（メタ）アクリルモノマー（Ｙ）及び多官能（メタ）アクリルモノマー（Ｚ）の合計含有率は、５０質量％～１００質量％であることが好ましく、７０質量％～１００質量％であることがより好ましく、９０質量％～１００質量％であることがさらに好ましい。 In the (meth)acrylic monomer component, the total content of mono(meth)acrylic monomer (X), di(meth)acrylic monomer (Y), and polyfunctional (meth)acrylic monomer (Z) is 50% by mass to 100% by mass. %, more preferably 70% to 100% by weight, even more preferably 90% to 100% by weight.
　組成物におけるシロキサン結合濃度が、０．１００ｍｍｏｌ／ｇ～３．０００ｍｍｏｌ／ｇであることが好ましく、０．３００ｍｍｏｌ／ｇ～２．５００ｍｍｏｌ／ｇであることがより好ましい。
　シロキサン結合濃度が０．１００ｍｍｏｌ／ｇ以上であることで離型性が向上する傾向にあり、３．０００ｍｍｏｌ／ｇ以下であることで鋳型内から有床義歯を取り出す際の破断を抑制でき、靱性に優れる傾向にある。 The siloxane bond concentration in the composition is preferably 0.100 mmol/g to 3.000 mmol/g, more preferably 0.300 mmol/g to 2.500 mmol/g.
When the siloxane bond concentration is 0.100 mmol/g or more, mold release properties tend to improve, and when it is 3.000 mmol/g or less, it is possible to suppress breakage when taking out the denture from the mold, and improve toughness. They tend to be excellent at
　（メタ）アクリルモノマー成分における芳香環濃度が、０．００１５ｍｏｌ／ｇ～０．００７０ｍｏｌ／ｇであることが好ましく、０．００２０ｍｏｌ／ｇ～０．００６５ｍｏｌ／ｇであることがより好ましい。 The aromatic ring concentration in the (meth)acrylic monomer component is preferably 0.0015 mol/g to 0.0070 mol/g, more preferably 0.0020 mol/g to 0.0065 mol/g.
　離型性及び靱性の観点から、組成物におけるシロキサン結合濃度及び（メタ）アクリルモノマー成分における芳香環濃度がそれぞれ前述の数値範囲を満たすことが好ましい。 From the viewpoint of mold releasability and toughness, it is preferable that the siloxane bond concentration in the composition and the aromatic ring concentration in the (meth)acrylic monomer component each satisfy the aforementioned numerical ranges.
　モノ（メタ）アクリルモノマー（Ｘ）、ジ（メタ）アクリルモノマー（Ｙ）、多官能（メタ）アクリルモノマー（Ｚ）及び光重合開始剤の合計含有量は、本開示の光硬化性組成物の全量に対し、８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることがさらに好ましい。
　モノ（メタ）アクリルモノマー（Ｘ）、ジ（メタ）アクリルモノマー（Ｙ）、多官能（メタ）アクリルモノマー（Ｚ）及び光重合開始剤の合計含有量の上限は特に限定されず、１００質量％以下であればよい。 The total content of the mono(meth)acrylic monomer (X), the di(meth)acrylic monomer (Y), the polyfunctional (meth)acrylic monomer (Z), and the photopolymerization initiator is the same as that of the photocurable composition of the present disclosure. It is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total amount.
The upper limit of the total content of mono(meth)acrylic monomer (X), di(meth)acrylic monomer (Y), polyfunctional (meth)acrylic monomer (Z), and photopolymerization initiator is not particularly limited, and is 100% by mass. The following is sufficient.
〔立体造形物〕
　本開示の立体造形物は、本開示の光硬化性組成物の硬化物を含む。
　このため、本開示の立体造形物が鋳型である場合、有床義歯の製造時における変形が抑制可能であり、鋳型を用いて有床義歯を製造する際に、鋳型内から有床義歯を取り出しやすくなる。
　本開示の立体造形物は、光造形による硬化物（即ち、光造形物）を含むことが好ましい。
　硬化物（例えば光造形物）を製造する方法については、前述したとおりである。
　立体造形物の好ましい態様としては、鋳型が挙げられ、より具体的には、有床義歯の製造に用いられる鋳型が挙げられる。 [Three-dimensional object]
The three-dimensional structure of the present disclosure includes a cured product of the photocurable composition of the present disclosure.
Therefore, when the three-dimensional molded object of the present disclosure is a mold, deformation during the production of the denture can be suppressed, and when the denture is manufactured using the mold, the denture is removed from the mold. It becomes easier.
It is preferable that the three-dimensional shaped article of the present disclosure includes a cured product obtained by stereolithography (i.e., a stereolithographic article).
The method for producing a cured product (for example, a stereolithographic product) is as described above.
A preferred embodiment of the three-dimensional structure includes a mold, and more specifically, a mold used for manufacturing a denture.
〔硬化物の製造方法〕
　本開示の硬化物の製造方法は、前述の鋳型内で硬化性組成物を重合させる工程を含む。例えば、前述の本開示の光硬化性組成物を用いて鋳型を作製し、作製された鋳型内に硬化性組成物を注入し、注入された硬化性組成物を重合させることで硬化物を作製すればよい。鋳型内に注入される硬化性組成物としては、熱、光等によって重合する重合性成分を含んでいれば特に限定されない。例えば、鋳型内に人工歯を配列して有床義歯を作製する場合、従来公知の義歯床作製用の硬化性組成物を鋳型内に注入し、注入後の義歯床作製用の硬化性組成物を硬化させてもよい。 [Method for producing cured product]
The method for producing a cured product of the present disclosure includes the step of polymerizing the curable composition in the mold described above. For example, a mold is produced using the photocurable composition of the present disclosure described above, the curable composition is injected into the produced mold, and the injected curable composition is polymerized to produce a cured product. do it. The curable composition injected into the mold is not particularly limited as long as it contains a polymerizable component that is polymerized by heat, light, or the like. For example, when making a denture by arranging artificial teeth in a mold, a conventionally known curable composition for making a denture base is injected into the mold, and the curable composition for making a denture base after injection is injected into the mold. may be cured.
〔有床義歯の製造方法〕
　本開示の有床義歯の製造方法は、光硬化性組成物を光造形により硬化させ、有床義歯の製造に用いられる鋳型を作製する工程と、前記鋳型内で硬化性組成物を重合させ、有床義歯を製造する工程と、を含む。
　本開示の有床義歯の製造方法では、鋳型を作製する工程及び有床義歯を製造する工程の２つの工程を経ることで有床義歯を製造する方法であり、従来の鋳型を用いた有床義歯の作製方法よりも簡便な方法で有床義歯を製造することができる。 [Method for manufacturing dentures]
The method for manufacturing a denture with a denture of the present disclosure includes a step of curing a photocurable composition by stereolithography to produce a mold used for manufacturing the denture with a denture, polymerizing the curable composition in the mold, A step of manufacturing a fixed denture.
The method for manufacturing a denture with a backing according to the present disclosure is a method of manufacturing a denture with a backing through two steps: a step of making a mold and a step of manufacturing a denture with a backing, and a method of manufacturing a denture with a backing using a conventional mold. A denture with a backing can be manufactured using a method that is simpler than a method for manufacturing a denture.
　鋳型を作製する工程は、例えば、有床義歯の使用者の口腔内における３次元印象データを取得する工程と、取得された３次元印象データから鋳型データを取得する工程と、取得された鋳型データに基づいて、光硬化性組成物を光造形により硬化させる工程と、を含むことが好ましい。 The process of producing a mold includes, for example, a process of acquiring three-dimensional impression data in the oral cavity of a denture user, a process of acquiring mold data from the acquired three-dimensional impression data, and a process of acquiring mold data. It is preferable to include a step of curing the photocurable composition by stereolithography based on.
　有床義歯を製造する工程は、鋳型に人工歯を配列する工程と、人工歯が鋳型内に配列された状態で義歯床作製用の硬化性組成物を鋳型に注入する工程と、注入後の硬化性組成物を硬化させる工程と、鋳型から製造された有床義歯を取り出す工程と、を含むことが好ましい。 The process of manufacturing dentures includes the steps of arranging artificial teeth in a mold, injecting a curable composition for making a denture base into the mold with the artificial teeth arranged in the mold, and post-injection steps. It is preferable to include the steps of curing the curable composition and removing the manufactured denture from the mold.
　本開示の有床義歯の製造方法では、鋳型の作製に用いられる光硬化性組成物は特に限定されない。例えば、注入後の硬化性組成物を硬化させる工程における鋳型の変形を抑制する観点及び鋳型から製造された有床義歯を取り出す工程における有床義歯、鋳型等の損傷を抑制する観点から、前述の本開示の光硬化性組成物を、鋳型の作製に用いられる光硬化性組成物として用いることが好ましい。 In the denture manufacturing method of the present disclosure, the photocurable composition used to create the mold is not particularly limited. For example, from the viewpoint of suppressing deformation of the mold in the process of curing the curable composition after injection, and from the viewpoint of suppressing damage to the denture, mold, etc. in the process of removing the denture manufactured from the mold, the above-mentioned It is preferable to use the photocurable composition of the present disclosure as a photocurable composition used for producing a mold.
　以下、本開示の実施例を示すが、本開示は以下の実施例には限定されない。 Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples.
〔実施例１～１９、比較例１～３〕
＜光硬化性組成物の調製＞
　表１～表３に示す各成分を混合し、光硬化性組成物を得た。表１では、各成分の詳細を示し、表２、及び表３では、各成分の混合比を示す。 [Examples 1 to 19, Comparative Examples 1 to 3]
<Preparation of photocurable composition>
The components shown in Tables 1 to 3 were mixed to obtain a photocurable composition. Table 1 shows details of each component, and Tables 2 and 3 show the mixing ratio of each component.
＜測定及び評価＞
　得られた光硬化性組成物を用い、以下の測定及び評価を行った。
　結果を表２及び表３に示す。 <Measurement and evaluation>
The following measurements and evaluations were performed using the obtained photocurable composition.
The results are shown in Tables 2 and 3.
（貯蔵弾性率）
　得られた光硬化性組成物に対し波長４０５ｎｍの可視光を照射量１１ｍＪ／ｃｍ２にて照射して厚み５０μｍの硬化層Ａ１を形成し、前記硬化層Ａ１を厚み方向に積層させることにより、長さ４０ｍｍ、幅１０ｍｍ、厚み１．０ｍｍの矩形板形状の造形物Ａ１を形成し、前記造形物Ａ１に対し、波長３６５ｎｍの紫外線を照射量３Ｊ／ｃｍ２にて照射する条件の光造形により、長さ４０ｍｍ、幅１０ｍｍ、厚み１．０ｍｍの矩形板形状の試験片Ａ１を作製した。
　作製された試験片Ａ１について、動的粘弾性測定により、昇温範囲２５℃～２００℃及び昇温速度３℃／分にて昇温しながら測定周波数１Ｈｚの条件にて測定し、２５℃における貯蔵弾性率及び３７℃における貯蔵弾性率を求めた。
　試験片Ａ１の作製は、ＤＬＰ方式の３Ｄプリンタ（Ｋｕｌｚｅｒ社、Ｃａｒａ　Ｐｒｉｎｔ４．０）を用いて行い、貯蔵弾性率の測定は、動的粘弾性測定装置（株式会社日立ハイテクサイエンス社製、ＤＭＡ７１００）を用いて行った。 (storage modulus)
By irradiating the obtained photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer A1 with a thickness of 50 μm, and laminating the cured layer A1 in the thickness direction, A rectangular plate-shaped object A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet rays with a wavelength of 365 nm at an irradiation amount of 3 J/cm 2 by stereolithography. A rectangular plate-shaped test piece A1 having a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was prepared.
The produced test piece A1 was measured by dynamic viscoelasticity measurement under the conditions of a measurement frequency of 1 Hz while increasing the temperature in a temperature range of 25°C to 200°C and a heating rate of 3°C/min. The storage modulus and the storage modulus at 37°C were determined.
The test piece A1 was prepared using a DLP 3D printer (Kulzer, Cara Print 4.0), and the storage modulus was measured using a dynamic viscoelasticity measurement device (DMA7100, Hitachi High-Tech Science Co., Ltd.). This was done using
（粘度）
　得られた光硬化性組成物の粘度を、Ｅ型粘度計により、２５℃、５０ｒｐｍの条件で測定した。
　その結果、実施例１～１９の光硬化性組成物の粘度は、いずれも５０ｍＰａ・ｓ～３０００ｍＰａ・ｓの範囲であった。 (viscosity)
The viscosity of the obtained photocurable composition was measured using an E-type viscometer at 25° C. and 50 rpm.
As a result, the viscosities of the photocurable compositions of Examples 1 to 19 were all in the range of 50 mPa·s to 3000 mPa·s.
（変形性）
　得られた光硬化性組成物に対し波長４０５ｎｍの可視光を照射量１１ｍＪ／ｃｍ２にて照射して厚み５０μｍの硬化層Ａ１を形成し、前記硬化層Ａ１を厚み方向に積層させることにより、図１に示す立体造形物Ａ２を形成し、前記造形物Ａ２に対し、波長３６５ｎｍの紫外線を照射量３Ｊ／ｃｍ２にて照射する条件の光造形により、図１に示す試験片Ａ２を作製した。
　図１に示すように、試験片Ａ２は、Ｌが２８ｍｍであり、Ｌ’が２０ｍｍであり、Ｗが２ｍｍであり、Ｈが２４ｍｍであり、Ｈ’が２２ｍｍであり、幅（Ｄ）が２ｍｍの隙間を有する形状である。有床義歯製作用（メタ）アクリレートポリマー粉及び（メタ）アクリレートモノマー液であるＰａｌａｐｒｅｓｓ（登録商標）　Ｖａｒｉｏ（Ｋｕｌｚｅｒ社製）を、粉体１０ｇ：液体７ｍＬの比で混合し、膨張段階（２３℃で約２分）後に、製造された試験片Ａ２の幅２ｍｍの隙間部に充填し、５５℃及び圧力２ｂａｒで３０分間重合させる。その後、試験片Ａ２の長さＬを、マイクロメーター（ミツトヨ社製、ＭＤＣ－２５ＰＸ）で測定し、設計値（２８ｍｍ）からのズレ（ｍｍ）を算出した。設計値からのズレが小さい程、有床義歯製作時の変形性に優れ、寸法精度に優れる。設計値からのズレが０．０５ｍｍ未満を「Ａ」、０．０５ｍｍ以上０．１０ｍｍ以下を「Ｂ」、０．１０ｍｍより大きい場合を「Ｃ」として評価した。 (Deformability)
By irradiating the obtained photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer A1 with a thickness of 50 μm, and laminating the cured layer A1 in the thickness direction, A three-dimensional model A2 shown in FIG . 1 was formed, and the test piece A2 shown in FIG. .
As shown in Figure 1, test piece A2 has L of 28 mm, L' of 20 mm, W of 2 mm, H of 24 mm, H' of 22 mm, and width (D) of 2 mm. The shape has a gap of . (Meth)acrylate polymer powder for making dentures and Palapress (registered trademark) Vario (manufactured by Kulzer), which is a (meth)acrylate monomer liquid, were mixed at a ratio of 10 g of powder to 7 mL of liquid, and the mixture was heated at an expansion stage (23°C). After about 2 minutes), the 2 mm wide gap of the produced test piece A2 was filled and polymerized at 55° C. and 2 bar pressure for 30 minutes. Thereafter, the length L of the test piece A2 was measured with a micrometer (manufactured by Mitutoyo, MDC-25PX), and the deviation (mm) from the design value (28 mm) was calculated. The smaller the deviation from the design value, the better the deformability and dimensional accuracy when manufacturing dentures. A deviation from the design value of less than 0.05 mm was evaluated as "A," a deviation of 0.05 mm or more and 0.10 mm or less was evaluated as "B," and a deviation larger than 0.10 mm was evaluated as "C."
（３７℃の脱着試験における形状回復性）
　得られた光硬化性組成物に対し波長４０５ｎｍの可視光を照射量１１ｍＪ／ｃｍ２にて照射して厚み５０μｍの硬化層Ａ１を形成し、前記硬化層Ａ１を厚み方向に積層させることにより、図２に示す立体造形物Ａ３を形成し、前記造形物Ａ３に対し、波長３６５ｎｍの紫外線を照射量３Ｊ／ｃｍ２にて照射する条件の光造形により、図２に示す試験片Ａ３を作製した。
　図２に示すように、試験片Ａ３は、Ｌが１５ｍｍであり、Ｌ’が２ｍｍであり、Ｈが１２ｍｍであり、Ｈ’が２ｍｍであり、Ｒが４ｍｍであり、厚み（Ｄ）が１０ｍｍの形状である。
　得られた試験片Ａ３の２つの半円柱の間に、鉄球（直径１０ｍｍ）を移動速度１２０．０±２．０ｍｍ／分の条件で出し入れし、着脱試験を行った。１０回の出し入れ移動後に、試験片を観察し、試験後に形状変化無し、及び割れ無しを「Ａ」、試験後に形状変化有り、割れ無しを「Ｂ」、試験後に割れ発生を「Ｃ」として評価した。 (Shape recovery in desorption test at 37°C)
By irradiating the obtained photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer A1 with a thickness of 50 μm, and laminating the cured layer A1 in the thickness direction, A three-dimensional object A3 shown in FIG. 2 was formed, and a test piece A3 shown in FIG. 2 was produced by stereolithography under conditions of irradiating the object A3 with ultraviolet light with a wavelength of 365 nm at an irradiation dose of 3 J/cm 2 . .
As shown in FIG. 2, test piece A3 has L of 15 mm, L' of 2 mm, H of 12 mm, H' of 2 mm, R of 4 mm, and thickness (D) of 10 mm. It has the shape of
An attachment/detachment test was conducted by inserting and removing an iron ball (diameter 10 mm) between the two semicircular columns of the obtained test piece A3 at a moving speed of 120.0±2.0 mm/min. Observe the test piece after moving it in and out 10 times, and evaluate it as "A" if there is no shape change and no cracking after the test, "B" if there is shape change and no cracking after the test, and "C" if cracking occurs after the test. did.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　表２及び表３中、各実施例及び各比較例における「組成」欄の数字は、質量部を意味し、空欄は、該当する成分を含有しないことを意味する。 In Tables 2 and 3, the numbers in the "Composition" column in each Example and each Comparative Example mean parts by mass, and a blank column means that the corresponding component is not contained.
＜ジ（メタ）アクリルモノマー（Ａ）＞
　表１～表３中、ジ（メタ）アクリルモノマー（Ａ）に分類される化合物は、具体的には下記光重合性成分１及び２である。 <Di(meth)acrylic monomer (A)>
In Tables 1 to 3, the compounds classified as di(meth)acrylic monomers (A) are specifically the following photopolymerizable components 1 and 2.
　光重合性成分１：エトキシ化ビスフェノールＡジアクリレート（Ａ－ＢＰＥ－１０、新中村化学工業株式会社）
　光重合性成分２：エトキシ化ビスフェノールＡジメタクリレート（ＢＰＥ－５００、新中村化学工業株式会社製） Photopolymerizable component 1: Ethoxylated bisphenol A diacrylate (A-BPE-10, Shin Nakamura Chemical Co., Ltd.)
Photopolymerizable component 2: Ethoxylated bisphenol A dimethacrylate (BPE-500, manufactured by Shin Nakamura Chemical Co., Ltd.)
＜（メタ）アクリルモノマー（Ｂ）＞
　表１～表３中、（メタ）アクリルモノマー（Ｂ）に分類される化合物は、具体的には下記光重合性成分３～１７である。
　光重合性成分３～９は、２つの（メタ）アクリロイルオキシ基と、芳香環及びウレタン結合の少なくとも一方と、を有し、距離ｄ１が、１０Å以上２５Å未満であるジ（メタ）アクリルモノマー（Ｂ－１）に分類される。
　光重合性成分１０は、２つの（メタ）アクリロイルオキシ基と、芳香環及びウレタン結合の少なくとも一方と、を有し、距離ｄ１が、８０Å超２００Å未満であるジ（メタ）アクリルモノマー（Ｂ－２）に分類される。
　光重合性成分１１～１７は、１つの（メタ）アクリロイルオキシ基と、芳香環及びヒドロキシ基の少なくとも一方と、を有するモノ（メタ）アクリルモノマー（Ｂ－３）に分類される。 <(meth)acrylic monomer (B)>
In Tables 1 to 3, the compounds classified as (meth)acrylic monomers (B) are specifically the following photopolymerizable components 3 to 17.
Photopolymerizable components 3 to 9 are di(meth)acrylic monomers (meth)acrylic monomers having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, and a distance d1 of 10 Å or more and less than 25 Å. Classified as B-1).
The photopolymerizable component 10 is a di(meth)acrylic monomer (B- It is classified as 2).
Photopolymerizable components 11 to 17 are classified as mono(meth)acrylic monomers (B-3) having one (meth)acryloyloxy group and at least one of an aromatic ring and a hydroxy group.
　光重合性成分３：エトキシ化ビスフェノールＡジアクリレート（ＢＰ－４ＥＡＬ、共栄社化学株式会社）
　光重合性成分４：エトキシ化ビスフェノールＡジメタクリレート（ＳＲ５４０、サートマー株式会社）
　光重合性成分５：エトキシ化ビスフェノールＦジアクリレート（Ｍ－２０８、東亞合成株式会社）
　光重合性成分６：エトキシ化ビスフェノールＡジメタクリレート（ＳＲ３４８、サートマー株式会社）
　光重合性成分７：ウレタンジアクリレート（ＳＵＡ－１（表中のＵＤＡ）、下記製造例１Ａに従って製造した化合物）
　光重合性成分８：ウレタンジメタクリレート（ＳＵＡ－２（表中のＵＤＭＡ）、下記製造例１Ｂに従って製造した化合物）
　光重合性成分９：２官能ウレタンアクリレート（ＡＨ－６００、共栄社化学株式会社）
　光重合性成分１０：多官能ウレタンアクリレート（ＳＵＡ－３（表中のＵＡ１）、下記製造例１Ｃに記載の方法により製造した化合物）
　光重合性成分１１：フェノキシエチルアクリレート（ＰＯ－Ａ、共栄社化学株式会社）
　光重合性成分１２：フェノキシエチルメタクリレート（ＰＯ、共栄社化学株式会社）
　光重合性成分１３：ｍ－フェノキシベンジルアクリレート（ＰＯＢ－Ａ、共栄社化学株式会社）
　光重合性成分１４：エトキシ化－ｏ－フェニルフェノールアクリレート（Ａ－ＬＥＮ－１０、新中村化学工業株式会社）
　光重合性成分１５：４－ヒドロキシブチルアクリレート（４－ＨＢＡ）
　光重合性成分１６：２－ヒドロキシプロピルアクリレート（ＨＯＰ－Ａ、共栄社化学株式会社）
　光重合性成分１７：２－ヒドロキシ－３－フェノキシプロピルアクリレート（Ｍ６００－Ａ、共栄社化学株式会社） Photopolymerizable component 3: Ethoxylated bisphenol A diacrylate (BP-4EAL, Kyoeisha Chemical Co., Ltd.)
Photopolymerizable component 4: Ethoxylated bisphenol A dimethacrylate (SR540, Sartomer Co., Ltd.)
Photopolymerizable component 5: Ethoxylated bisphenol F diacrylate (M-208, Toagosei Co., Ltd.)
Photopolymerizable component 6: Ethoxylated bisphenol A dimethacrylate (SR348, Sartomer Co., Ltd.)
Photopolymerizable component 7: Urethane diacrylate (SUA-1 (UDA in the table), compound produced according to Production Example 1A below)
Photopolymerizable component 8: Urethane dimethacrylate (SUA-2 (UDMA in the table), compound produced according to Production Example 1B below)
Photopolymerizable component 9: Bifunctional urethane acrylate (AH-600, Kyoeisha Chemical Co., Ltd.)
Photopolymerizable component 10: polyfunctional urethane acrylate (SUA-3 (UA1 in the table), a compound produced by the method described in Production Example 1C below)
Photopolymerizable component 11: Phenoxyethyl acrylate (PO-A, Kyoeisha Chemical Co., Ltd.)
Photopolymerizable component 12: Phenoxyethyl methacrylate (PO, Kyoeisha Chemical Co., Ltd.)
Photopolymerizable component 13: m-phenoxybenzyl acrylate (POB-A, Kyoeisha Chemical Co., Ltd.)
Photopolymerizable component 14: Ethoxylated-o-phenylphenol acrylate (A-LEN-10, Shin Nakamura Chemical Co., Ltd.)
Photopolymerizable component 15: 4-hydroxybutyl acrylate (4-HBA)
Photopolymerizable component 16: 2-hydroxypropyl acrylate (HOP-A, Kyoeisha Chemical Co., Ltd.)
Photopolymerizable component 17: 2-hydroxy-3-phenoxypropyl acrylate (M600-A, Kyoeisha Chemical Co., Ltd.)
＜その他モノマー＞
　表１～表３中、その他モノマーに分類される化合物は、具体的には下記光重合性成分１８及び１９である。
　光重合性成分１８：エトキシ化水添ビスフェノールＡジメタクリレート（ＨＢＰＥＭ－１０、第一工業製薬株式会社）
　光重合性成分１９：エトキシ化水添ビスフェノールＡジアクリレート（ＨＢＰＥ－４、第一工業製薬株式会社） <Other monomers>
In Tables 1 to 3, the compounds classified as other monomers are specifically the following photopolymerizable components 18 and 19.
Photopolymerizable component 18: Ethoxylated hydrogenated bisphenol A dimethacrylate (HBPEM-10, Daiichi Kogyo Seiyaku Co., Ltd.)
Photopolymerizable component 19: Ethoxylated hydrogenated bisphenol A diacrylate (HBPE-4, Daiichi Kogyo Seiyaku Co., Ltd.)
＜光重合開始剤＞
　表１～表３中、光重合開始剤に分類される化合物は、具体的には下記光重合開始剤１及び２である。 <Photopolymerization initiator>
In Tables 1 to 3, the compounds classified as photoinitiators are specifically the following photoinitiators 1 and 2.
　光重合開始剤１：アシルフォスフィンオキサイド系化合物（Ｏｍｎｉｒａｄ　８１９：ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製「Ｏｍｎｉｒａｄ　８１９」）
　光重合開始剤２：アシルフォスフィンオキサイド系化合物（Ｏｍｎｉｒａｄ　ＴＰＯ：ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製「Ｏｍｎｉｒａｄ　ＴＰＯ」） Photoinitiator 1: Acylphosphine oxide compound (Omnirad 819: “Omnirad 819” manufactured by IGM Resins B.V.)
Photoinitiator 2: Acylphosphine oxide compound (Omnirad TPO: “Omnirad TPO” manufactured by IGM Resins B.V.)
［製造例１Ａ：ＳＵＡ－１の製造］
　十分に乾燥させた撹拌羽根、及び温度計を備えた1リットル４ツ口フラスコ内に、ＨＥＡ（２－ヒドロキシエチルアクリレート）３７２ｇ（３．２０モル）、ＤＢＴＤＬ（ジラウリン酸ジブチル錫）０．７１ｇ（ＨＥＡとＴＭＨＤＩの合計質量に対して０．１質量％）、及びＭＥＨＱ（４－メトキシフェノール）０．３５ｇ（ＨＥＡとＴＭＨＤＩの合計質量に対して０．０５質量％）を添加し、均一となるまで撹拌した後、６０℃に昇温した。続いて、ＴＭＨＤＩ（トリメチルヘキサメチレンジイソシアナート）３３７ｇ（１．６０モル）を１時間かけて滴下した。滴下中に反応熱により内温が上昇したので、８０℃以下となるように滴下量をコントロールした。全量滴下後反応温度を８０℃に保って、１０時間反応を行った。この際、ＨＰＬＣ分析で反応の進行を追跡して、反応の終点を確認した。反応器から生成物を排出することにより、２官能ウレタンアクリレート（ＳＵＡ－１）６８０ｇを得た。２５℃における粘度は７１００ｍＰａ・ｓであった。 [Production Example 1A: Production of SUA-1]
In a 1 liter 4-necked flask equipped with a thoroughly dried stirring blade and a thermometer, 372 g (3.20 mol) of HEA (2-hydroxyethyl acrylate) and 0.71 g (dibutyltin dilaurate) of Add 0.1% by mass based on the total mass of HEA and TMHDI) and 0.35 g of MEHQ (4-methoxyphenol) (0.05% by mass based on the total mass of HEA and TMHDI) to make it uniform. After stirring until the temperature reached 60°C. Subsequently, 337 g (1.60 mol) of TMHDI (trimethylhexamethylene diisocyanate) was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 10 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 680 g of difunctional urethane acrylate (SUA-1) was obtained. The viscosity at 25°C was 7100 mPa·s.
［製造例１Ｂ：ＳＵＡ－２の製造］
　十分に乾燥させた撹拌羽根、及び温度計を備えた１リットル４ツ口フラスコ内に、ＨＥＭＡ（ヒドロキシエチルメタクリレート）４１６ｇ（３．２０モル）、ＤＢＴＤＬ　０．７５ｇ（ＨＥＡとＴＭＨＤＩの合計質量に対して０．１質量％）、及びＭＥＨＱ　０．３８ｇ（ＨＥＡとＴＭＨＤＩの合計質量に対して０．０５質量％）を添加し、均一となるまで撹拌した後、６０℃に昇温した。続いて、ＴＭＨＤＩ　３３７ｇ（１．６０モル）を１時間かけて滴下した。滴下中に反応熱により内温が上昇したので、８０℃以下となるように滴下量をコントロールした。全量滴下後反応温度を８０℃に保って、１０時間反応を行った。この際、ＨＰＬＣ分析で反応の進行を追跡して、反応の終点を確認した。反応器から生成物を排出することにより、２官能ウレタンアクリレート（ＳＵＡ－２）７２０ｇを得た。２５℃における粘度は８２００ｍＰａ・ｓであった。 [Production Example 1B: Production of SUA-2]
In a 1 liter 4-necked flask equipped with a sufficiently dried stirring blade and a thermometer, 416 g (3.20 mol) of HEMA (hydroxyethyl methacrylate) and 0.75 g of DBTDL (based on the total mass of HEA and TMHDI) were placed. 0.1% by mass) and 0.38 g of MEHQ (0.05% by mass based on the total mass of HEA and TMHDI) were added, stirred until homogeneous, and then heated to 60°C. Subsequently, 337 g (1.60 mol) of TMHDI was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 10 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 720 g of difunctional urethane acrylate (SUA-2) was obtained. The viscosity at 25°C was 8200 mPa·s.
［製造例１Ｃ：ＳＵＡ－３の製造］
　十分に乾燥させた撹拌羽根、及び温度計を備えた１リットル４ツ口フラスコ内に、ＩＰＤＩ（イソホロンジイソシアネート）２２２ｇ（１．００モル）、ＤＢＴＤＬ　０．８４ｇ（ＩＰＤＩ、ＰＥＧ－１０００及びＨＥＡの合計質量に対して０．１質量％）、及びＭＥＨＱ　０．４２ｇ（ＩＰＤＩ、ＰＥＧ－１０００及びＨＥＡの合計質量に対して０．０５質量％）を添加し、均一となるまで撹拌した後、６０℃に昇温した。続いて、ＰＴＭＧ１０００（分子量１０００、三菱ケミカル株式会社製）５００ｇ（０．５０モル）を１時間かけて滴下した。滴下中に反応熱により内温が上昇したので、８０℃以下となるように滴下量をコントロールした。全量滴下後反応温度を８０℃に保って、５時間反応を行った。
　続いて、フラスコの内温を６０℃に保持し、別の滴下漏斗に添加したＨＥＡ　１１６ｇ（１．００モル）を１時間かけて滴下した。滴下中に反応熱により内温が上昇したので、８０℃以下となるように滴下量をコントロールした。全量滴下後反応温度を８０℃に保って、５時間反応を行った。この際、ＨＰＬＣ分析で反応の進行を追跡して、反応の終点を確認した。反応器から生成物を排出することにより、ウレタンアクリレート（ＳＵＡ－３）８４０ｇを得た。４０℃における粘度は４１０００ｍＰａ・ｓであった。 [Production Example 1C: Production of SUA-3]
In a 1 liter 4-necked flask equipped with a sufficiently dried stirring blade and a thermometer, 222 g (1.00 mol) of IPDI (isophorone diisocyanate) and 0.84 g of DBTDL (total of IPDI, PEG-1000 and HEA) were added. 0.1% by mass based on the mass) and 0.42g of MEHQ (0.05% by mass based on the total mass of IPDI, PEG-1000 and HEA), stirred until homogeneous, and heated to 60°C. The temperature rose to . Subsequently, 500 g (0.50 mol) of PTMG1000 (molecular weight 1000, manufactured by Mitsubishi Chemical Corporation) was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 5 hours.
Subsequently, the internal temperature of the flask was maintained at 60° C., and 116 g (1.00 mol) of HEA, which had been added to another dropping funnel, was added dropwise over 1 hour. During the dropping, the internal temperature rose due to the heat of reaction, so the amount of dropping was controlled to keep it below 80°C. After dropping the entire amount, the reaction temperature was maintained at 80°C and the reaction was carried out for 5 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 840 g of urethane acrylate (SUA-3) was obtained. The viscosity at 40°C was 41000 mPa·s.
　表２及び表３に示すように、実施例において、変形性に優れ、かつ、形状回復性に優れた硬化物を得ることができた。
　一方、比較例１及び２において得られた硬化物は変形しやすく、比較例３において得られた硬化物は形状が回復しなかった。 As shown in Tables 2 and 3, in the Examples, cured products with excellent deformability and shape recovery properties could be obtained.
On the other hand, the cured products obtained in Comparative Examples 1 and 2 were easily deformed, and the cured products obtained in Comparative Example 3 did not recover their shape.
〔実施例２０〕
＜有床義歯の製造＞
　上顎もしくは下顎の石膏模型をラボ用デンタルスキャナー（Ｋｕｌｚｅｒ社、Ｃａｒａ　Ｓｃａｎ４．０）を用いてそれぞれ３次元印象データとした。市販のＣＡＤソフト（3DSystems社製、Geomagic Design X）にそれぞれの３次元印象データをアップロードした。ＣＡＤソフトウェア上で有床義歯製造用の鋳型のデザインを行い、鋳型の厚みを２．０ｍｍに設定し、３次元造形データを得た。
　実施例１の光硬化性組成物に対し、波長４０５ｎｍの可視光を照射量１１ｍＪ／ｃｍ２にて照射して厚み５０μｍの硬化層を形成し、前記硬化層を厚み方向に積層し、上記で得られた鋳型の３次元造形データを用いて造形することで有床義歯製造用鋳型造形物を得た。得られた鋳型造形物に対し、３Ｊ／ｃｍ２の条件で波長３６５ｎｍの紫外線を照射して造形物を本硬化させることにより、有床義歯製造用の鋳型を得た。 [Example 20]
<Manufacture of dentures>
A plaster model of the upper or lower jaw was used as three-dimensional impression data using a laboratory dental scanner (Kulzer, Cara Scan 4.0). Each three-dimensional impression data was uploaded to commercially available CAD software (3D Systems, Geomagic Design X). A mold for manufacturing dentures was designed on CAD software, the thickness of the mold was set to 2.0 mm, and three-dimensional modeling data was obtained.
The photocurable composition of Example 1 was irradiated with visible light with a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer with a thickness of 50 μm, and the cured layers were laminated in the thickness direction, and the above By modeling using the three-dimensional modeling data of the obtained mold, a molded article for manufacturing dentures with a base was obtained. The resulting molded article was irradiated with ultraviolet rays with a wavelength of 365 nm under conditions of 3 J/cm 2 to fully cure the article, thereby obtaining a mold for manufacturing dentures.
　上記で得られた有床義歯製造用の鋳型に人工歯を配列し、有床義歯製作用（メタ）アクリレートポリマー粉および（メタ）アクリレートモノマー液　（Ｋｕｌｚｅｒ社製，　Ｐａｌａｐｒｅｓｓ（登録商標）　Ｖａｒｉｏ）を所定の割合で混合し、人工歯が配列した鋳型に注入した。その後、石膏模型で蓋をして、５５℃及び圧力２ｂａｒで３０分間重合させた。重合後、鋳型及び石膏模型を取り除き、有床義歯を得た。このとき、鋳型及び有床義歯がともに損傷していないことが確認できた。
　なお、本手法は従来のろう義歯、シリコーン等を用いた手作業による方法より簡便に有床義歯を得ることができ、光造形には不適切な義歯用レジンを有床義歯の作製に用いることができるため、所望の物性を得ることに適している。 Artificial teeth were arranged in the mold for producing dentures obtained above, and (meth)acrylate polymer powder and (meth)acrylate monomer liquid for producing dentures (manufactured by Kulzer, Palapress (registered trademark) Vario) were added. The mixture was mixed at a predetermined ratio and injected into a mold containing an array of artificial teeth. It was then covered with a plaster cast and allowed to polymerize for 30 minutes at 55° C. and 2 bar pressure. After polymerization, the mold and plaster model were removed to obtain a denture. At this time, it was confirmed that both the mold and the denture were not damaged.
Note that this method allows for the creation of dentures more easily than conventional wax dentures, manual methods using silicone, etc., and the use of denture resin, which is unsuitable for stereolithography, for the production of dentures. Therefore, it is suitable for obtaining desired physical properties.
〔実施例２０～４３、比較例４～８〕
＜光硬化性組成物の調製＞
　表４～表７に示す各成分を混合し、光硬化性組成物を得た。表４では、各成分の詳細を示し、表５～表７では、各成分の混合比を示す。 [Examples 20 to 43, Comparative Examples 4 to 8]
<Preparation of photocurable composition>
The components shown in Tables 4 to 7 were mixed to obtain a photocurable composition. Table 4 shows the details of each component, and Tables 5 to 7 show the mixing ratio of each component.
＜測定及び評価＞
　得られた光硬化性組成物を用い、以下の測定及び評価を行った。既に説明した物性等の測定方法及び評価方法については省略する。
　結果を表５～表７に示す。 <Measurement and evaluation>
The following measurements and evaluations were performed using the obtained photocurable composition. The methods for measuring and evaluating the physical properties that have already been explained will be omitted.
The results are shown in Tables 5 to 7.
（デンチャーに対する離型性）
　得られた光硬化性組成物に対し波長４０５ｎｍの可視光を照射量１１ｍＪ／ｃｍ２にて照射して厚み５０μｍの硬化層Ａ１を形成し、前記硬化層Ａ１を厚み方向に積層させることにより、図３に示す立体造形物Ａ４を形成し、前記造形物Ａ４に対し、波長３６５ｎｍの紫外線を照射量３Ｊ／ｃｍ２にて照射する条件の光造形により、図３に示す試験片Ａ４を作製した。
　図３に示すように、試験片Ａ４は、Ｌが２４ｍｍであり、Ｌ’が２０ｍｍであり、Ｗが２ｍｍであり、Ｈが５ｍｍであり、Ｈ’が３ｍｍであり、Ｄが１４ｍｍであり、Ｄ’が１０ｍｍの形状である。有床義歯製作用（メタ）アクリレートポリマー粉及び（メタ）アクリレートモノマー液であるＰａｌａｐｒｅｓｓ（登録商標）　Ｖａｒｉｏ（Ｋｕｌｚｅｒ社製）を、粉体１０ｇ：液体７ｍＬの比で混合し、混合後１５秒後に、製造された試験片Ａ４のＬ’（２０ｍｍ）×Ｄ’（１０ｍｍ）×Ｈ’（３ｍｍ）からなる空間に混合物を充填し、５５℃及び圧力２ｂａｒで３０分間重合させる。その後、試験片Ａ４を有床義歯製作用重合体から剥がすように取り外す。その後、有床義歯製作用重合体の試験片Ａ４と接していた面を３Ｄ形状計測機（キーエンス社製、ＶＲ－３２００）により観察し、取り外した後の有床義歯製作用重合体に付着している試験片Ａ４の面積値を算出し、Ｌ’とＤ’からなる面（２００ｍｍ２）に対する付着率を算出した。付着率が小さい程、離型性に優れる。表面付着が無い場合を「Ａ」、表面付着が５％未満の場合を「Ｂ」、表面付着が５％以上の場合を「Ｃ」として評価した。 (Mold releasability for denture)
By irradiating the obtained photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer A1 with a thickness of 50 μm, and laminating the cured layer A1 in the thickness direction, A three-dimensional object A4 shown in FIG. 3 was formed, and a test piece A4 shown in FIG. 3 was produced by stereolithography under conditions of irradiating the object A4 with ultraviolet light with a wavelength of 365 nm at an irradiation dose of 3 J/cm 2 . .
As shown in FIG. 3, in the test piece A4, L is 24 mm, L' is 20 mm, W is 2 mm, H is 5 mm, H' is 3 mm, and D is 14 mm. It has a shape in which D' is 10 mm. (Meth)acrylate polymer powder for making dentures and Palapress (registered trademark) Vario (manufactured by Kulzer), which is a (meth)acrylate monomer liquid, were mixed at a ratio of 10 g of powder: 7 mL of liquid, and 15 seconds after mixing. The mixture is filled into the space of L' (20 mm) x D' (10 mm) x H' (3 mm) of the manufactured test piece A4, and polymerized for 30 minutes at 55° C. and 2 bar pressure. Thereafter, test piece A4 is peeled off from the denture manufacturing polymer. After that, the surface of the polymer for making dentures that was in contact with test piece A4 was observed using a 3D shape measuring machine (Keyence Corporation, VR-3200), and the surface that was in contact with the polymer for making dentures after being removed was observed. The area value of test piece A4 was calculated, and the adhesion rate to the surface (200 mm 2 ) consisting of L' and D' was calculated. The smaller the adhesion rate, the better the mold releasability. The evaluation was made as "A" when there was no surface adhesion, "B" when surface adhesion was less than 5%, and "C" when surface adhesion was 5% or more.
（離型時の靭性（取り外しやすさ））
　得られた光硬化性組成物に対し波長４０５ｎｍの可視光を照射量１１ｍＪ／ｃｍ２にて照射して厚み５０μｍの硬化層Ａ１を形成し、前記硬化層Ａ１を厚み方向に積層させることにより、図３に示す立体造形物Ａ４を形成し、前記造形物Ａ４に対し、波長３６５ｎｍの紫外線を照射量３Ｊ／ｃｍ２にて照射する条件の光造形により、図３に示す試験片Ａ４を作製した。
　図３に示すように、試験片Ａ４は、Ｌが２４ｍｍであり、Ｌ’が２０ｍｍであり、Ｗが２ｍｍであり、Ｈが５ｍｍであり、Ｈ’が３ｍｍであり、Ｄが１４ｍｍであり、Ｄ’が１０ｍｍの形状である。有床義歯製作用（メタ）アクリレートポリマー粉及び（メタ）アクリレートモノマー液であるＰａｌａｐｒｅｓｓ（登録商標）　Ｖａｒｉｏ（Ｋｕｌｚｅｒ社製）を、粉体１０ｇ：液体７ｍＬの比で混合し、混合後１５秒後に、製造された試験片Ａ４のＬ’（２０ｍｍ）×Ｄ’（１０ｍｍ）×Ｈ’（３ｍｍ）からなる空間に混合物を充填し、５５℃及び圧力２ｂａｒで３０分間重合させる。その後、試験片Ａ４を有床義歯製作用重合体から剥がすように取り外す。取り外した後の試験片Ａ４の外観を観察し、破断が無い場合を「Ａ」、破断が有る場合を「Ｂ」として評価した。 (Toughness during mold release (ease of removal))
By irradiating the obtained photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 to form a cured layer A1 with a thickness of 50 μm, and laminating the cured layer A1 in the thickness direction, A three-dimensional object A4 shown in FIG. 3 was formed, and a test piece A4 shown in FIG. 3 was produced by stereolithography under conditions of irradiating the object A4 with ultraviolet light with a wavelength of 365 nm at an irradiation dose of 3 J/cm 2 . .
As shown in FIG. 3, in the test piece A4, L is 24 mm, L' is 20 mm, W is 2 mm, H is 5 mm, H' is 3 mm, and D is 14 mm. It has a shape in which D' is 10 mm. (Meth)acrylate polymer powder for making dentures and Palapress (registered trademark) Vario (manufactured by Kulzer), which is a (meth)acrylate monomer liquid, were mixed at a ratio of 10 g of powder: 7 mL of liquid, and 15 seconds after mixing. The mixture is filled into the space of L' (20 mm) x D' (10 mm) x H' (3 mm) of the manufactured test piece A4, and polymerized for 30 minutes at 55° C. and 2 bar pressure. Thereafter, test piece A4 is peeled off from the denture manufacturing polymer. The appearance of test piece A4 after being removed was observed, and the case where there was no breakage was evaluated as "A", and the case where there was breakage was evaluated as "B".
（形状回復速度）
　得られた光硬化性組成物を、３Ｄプリンタ（Ｋｕｌｚｅｒ社、Ｃａｒａ　Ｐｒｉｎｔ４．０）を用い、可視光の波長４０５ｎｍ及び可視光の照度８．０ｍＪ／ｃｍ２の条件で、縦８ｍｍ×横３９ｍｍ×厚さ４ｍｍに造形して造形物（積層幅５０μｍ）を得た。
　得られた造形物に対し、１０Ｊ／ｃｍ２の条件で波長３６５ｎｍの紫外線を照射して造形物を本硬化させることにより、光造形物を得た。
　得られた光造形物（以下「試験片」という）について、試験片の長軸方向（横軸方向）における両端同士が接触するように応力を加えて試験片を湾曲させ、１０秒間保持した。その後応力を開放して試験片の形状変化を観察し、以下の基準で評価を行った。
　Ａ：応力開放後、１秒以内に元の形状に戻った
　Ｂ：応力開放後、元の形状に戻るまでに1秒以上有した (Shape recovery speed)
The obtained photocurable composition was printed using a 3D printer (Kulzer, Cara Print 4.0) to a size of 8 mm long x 39 mm wide under the conditions of a visible light wavelength of 405 nm and a visible light illuminance of 8.0 mJ/ cm2. A molded article (layer width 50 μm) was obtained by molding to a thickness of 4 mm.
An optically shaped article was obtained by irradiating the obtained article with ultraviolet rays with a wavelength of 365 nm under conditions of 10 J/cm 2 to fully cure the article.
Regarding the obtained stereolithographic object (hereinafter referred to as "test piece"), stress was applied to curve the test piece so that both ends of the test piece in the longitudinal direction (horizontal direction) were in contact with each other, and the test piece was held for 10 seconds. Thereafter, the stress was released and changes in the shape of the test piece were observed and evaluated based on the following criteria.
A: It returned to its original shape within 1 second after stress was released. B: It took more than 1 second to return to its original shape after stress was released.
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
　表５～表７中、各実施例及び各比較例における「組成」欄の数字は、質量部を意味し、空欄は、該当する成分を含有しないことを意味する。
　表５～表７中、各成分の詳細は以下の通りである。 In Tables 5 to 7, the numbers in the "Composition" column for each Example and each Comparative Example mean parts by mass, and a blank column means that the corresponding component is not contained.
Details of each component in Tables 5 to 7 are as follows.
＜モノ（メタ）アクリルモノマー（Ｘ）＞
　表４～表７に記載の、モノ（メタ）アクリルモノマー（Ｘ）の各々の構造は以下のとおりである。
ＰＯ－Ａ　　　　　共栄社化学株式会社製
ＰＯ　　　　　　　共栄社化学株式会社製
Ｐ２Ｈ－Ａ　　　　共栄社化学株式会社製
Ｍ－６００Ａ　　　共栄社化学株式会社製
ＰＯＢ－Ａ　　　　共栄社化学株式会社製
Ａ－ＬＥＮ－１０　新中村化学工業株式会社製 <Mono(meth)acrylic monomer (X)>
The structure of each mono(meth)acrylic monomer (X) listed in Tables 4 to 7 is as follows.
PO-A manufactured by Kyoeisha Chemical Co., Ltd. PO manufactured by Kyoeisha Chemical Co., Ltd. P2H-A manufactured by Kyoeisha Chemical Co., Ltd. M-600A manufactured by Kyoeisha Chemical Co., Ltd. POB-A manufactured by Kyoeisha Chemical Co., Ltd. A-LEN-10 manufactured by Shin Nakamura Chemical Co., Ltd.
＜ジ（メタ）アクリルモノマー（Ｙ）＞
　表４～表７に記載の、ジ（メタ）アクリルモノマー（Ｙ）の各々の構造は以下のとおりである。
ＳＵＡ－１　　　　下記製造例１Ａに記載の方法により製造した化合物（表中のＵＤＡ）
ＡＢＥ－３００　　新中村化学工業株式会社製
Ａ－ＢＰＥ－１０　新中村化学工業株式会社製
ＳＡ－００１　　　下記製造例２Ａに記載の方法により製造した化合物
ＡＨ－６００　　　共栄社化学株式会社製
ＳＡ－００２　　　下記製造例２Ｂに記載の方法により製造した化合物
ＳＵＡ－３　　　　下記製造例１Ｃに記載の方法により製造した化合物（表中のＵＡ１） <Di(meth)acrylic monomer (Y)>
The structure of each di(meth)acrylic monomer (Y) listed in Tables 4 to 7 is as follows.
SUA-1 Compound produced by the method described in Production Example 1A below (UDA in the table)
ABE-300 A-BPE-10 manufactured by Shin Nakamura Chemical Co., Ltd. SA-001 manufactured by Shin Nakamura Chemical Co., Ltd. Compound AH-600 manufactured by the method described in Production Example 2A below AH-600 manufactured by Kyoeisha Chemical Co., Ltd. SA-002 manufactured below Compound SUA-3 produced by the method described in Example 2B Compound produced by the method described in Production Example 1C below (UA1 in the table)
［製造例２Ａ：ＳＡ－００１の製造］
　十分に乾燥させた撹拌羽根、及び温度計を備えた２リットル４ツ口フラスコ内に、ペンタンジオール１７０．８１ｇ（１．６４モル）、無水フタル酸１２０．８ｇ（０．８２モル）、ｐ－トルエンスルホン酸３．６ｇ、フェノチアジン０．５ｇ、トルエン３００ｇを仕込み、窒素雰囲気下、１５０～２００℃に加熱し、５時間反応を行った。その後アクリル酸１２２．５０ｇ（１．７０モル）を仕込みさらに過熱し、１０時間反応を行った。反応生成物をトルエン５００ｇに溶解し、１０％ＮａＯＨ水溶液で中和した後、５％硫酸アンモニウム水溶液１５０ｇで洗浄した。トルエンを減圧蒸留して、ジ（メタ）アクリルモノマー（ＳＡ－００１）３９０ｇを得た。２５℃における粘度は４１０ｍＰａ・ｓであった。 [Production Example 2A: Production of SA-001]
In a 2 liter 4-necked flask equipped with a thoroughly dried stirring blade and a thermometer, 170.81 g (1.64 mol) of pentanediol, 120.8 g (0.82 mol) of phthalic anhydride, p- 3.6 g of toluenesulfonic acid, 0.5 g of phenothiazine, and 300 g of toluene were charged, heated to 150 to 200° C. under a nitrogen atmosphere, and reacted for 5 hours. Thereafter, 122.50 g (1.70 mol) of acrylic acid was charged, and the mixture was further heated and reacted for 10 hours. The reaction product was dissolved in 500 g of toluene, neutralized with 10% NaOH aqueous solution, and then washed with 150 g of 5% ammonium sulfate aqueous solution. Toluene was distilled under reduced pressure to obtain 390 g of di(meth)acrylic monomer (SA-001). The viscosity at 25°C was 410 mPa·s.
［製造例２Ｂ：ＳＡ－００２の製造］
　撹拌装置、空気導入管、及び温度計を備えた四ツ口フラスコに、カプロラクトン変性２－ヒドロキシエチルアクリレート（商品名「プラクセルＦＡ２Ｄ」、株式会社ダイセル製、カプロラクトン平均付加モル数２）３４４ｇ（１．００モル）、ジシクロヘキシルメタン４，４’－ジイソシアナート１３１ｇ（０．５０モル）、ＤＢＴＤＬ（ジラウリン酸ジブチル錫）０．８４ｇ、及びＭＥＨＱ（４－メトキシフェノール）０．４２ｇを添加し、８０℃で１２時間反応させた。この際、ＨＰＬＣ分析で反応の進行を追跡して、反応の終点を確認した。反応器から生成物を排出することにより、ジ（メタ）アクリルモノマー（ＳＡ－００２）４５１ｇを得た。２５℃における粘度は１２０００ｍＰａ・ｓであった。 [Production Example 2B: Production of SA-002]
In a four-necked flask equipped with a stirrer, an air inlet tube, and a thermometer, 344 g (1. 00 mol), dicyclohexylmethane 4,4'-diisocyanate 131 g (0.50 mol), DBTDL (dibutyltin dilaurate) 0.84 g, and MEHQ (4-methoxyphenol) 0.42 g were added, and the mixture was heated at 80°C. The mixture was allowed to react for 12 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. By discharging the product from the reactor, 451 g of di(meth)acrylic monomer (SA-002) was obtained. The viscosity at 25°C was 12000 mPa·s.
＜多官能（メタ）アクリルモノマー（Ｚ）＞
　表４～表７に記載の、多官能（メタ）アクリルモノマー（Ｚ）の各々の構造は以下のとおりである。
ＳｉＡ－００１　下記製造例２Ｃに記載の方法により製造した化合物
ＳｉＡ－００２　下記製造例２Ｄに記載の方法により製造した化合物
ＳｉＡ－００３　下記製造例２Ｅに記載の方法により製造した化合物 <Polyfunctional (meth)acrylic monomer (Z)>
The structure of each of the polyfunctional (meth)acrylic monomers (Z) listed in Tables 4 to 7 is as follows.
SiA-001 Compound manufactured by the method described in Production Example 2C below SiA-002 Compound manufactured by the method described in Production Example 2D below SiA-003 Compound produced by the method described in Production Example 2E below
［製造例２Ｃ：ＳｉＡ－００１の製造］
　十分に乾燥させた撹拌羽根、及び温度計を備えた１リットル４ツ口フラスコ内に、３，３’－（１，１，３，３，５，５－Ｈｅｘａｍｅｔｈｙｌ－１，５－ｔｒｉｓｉｌｏｘａｎｅｄｉｙｌ）ｂｉｓ［１－ｐｒｏｐａｎｏｌ］　３２４ｇ（１．００モル）、ＢＨＴ０．３０ｇ、及び酢酸エチル５００ｇを添加し、均一となるまで撹拌した後、７０℃に昇温した。続いて、アクリロイルクロリド１８１ｇ（２．００モル）を１時間かけて滴下した。滴下中に反応熱により内温が上昇したので、７０℃以下となるように滴下量をコントロールした。全量滴下後反応温度を７０℃に保って、５時間反応を行った。その後、反応溶液を１０％ＮａＯＨ水溶液で中和した後、５％硫酸アンモニウム水溶液１５０ｇで洗浄した。酢酸エチルを減圧蒸留して、多官能（メタ）アクリルモノマー（ＳｉＡ－００１）４４０ｇを得た。２５℃における粘度は１１０ｍＰａ・ｓであった。 [Production Example 2C: Production of SiA-001]
3,3'-(1,1,3,3,5,5-Hexamethyl-1,5-trisiloxanediyl) bis into a 1 liter 4-necked flask equipped with a thoroughly dried stirring blade and a thermometer. 324 g (1.00 mol) of [1-propanol], 0.30 g of BHT, and 500 g of ethyl acetate were added, stirred until homogeneous, and then heated to 70°C. Subsequently, 181 g (2.00 mol) of acryloyl chloride was added dropwise over 1 hour. Since the internal temperature rose due to reaction heat during the dropping, the dropping amount was controlled to be 70°C or less. After dropping the entire amount, the reaction temperature was maintained at 70°C and the reaction was carried out for 5 hours. Thereafter, the reaction solution was neutralized with a 10% NaOH aqueous solution, and then washed with 150 g of a 5% ammonium sulfate aqueous solution. Ethyl acetate was distilled under reduced pressure to obtain 440 g of polyfunctional (meth)acrylic monomer (SiA-001). The viscosity at 25°C was 110 mPa·s.
［製造例２Ｄ：ＳｉＡ－００２の製造］
　十分に乾燥させた撹拌羽根、及び温度計を備えた１リットル４ツ口フラスコ内に、１，３－Ｂｉｓ（３－ｃｈｌｏｒｏｐｒｏｐｙｌ）－１，１，３，３－ｔｅｔｒａｍｅｔｈｙｌｄｉｓｉｌｏｘａｎｅ２８７ｇ（１．００モル）、ＢＨＴ０．３０ｇ及びトルエン５００ｇを添加し、均一となるまで撹拌した後、６０℃に昇温した。続いて、オクタメチルシクロテトラシロキサン５９３ｇ（２．００モル）を１時間かけて滴下した。全量滴下後反応温度を６０℃に保って、６時間反応を行った。その後、オクタエチレングリコール７４０ｇ（２．００モル）を反応容器に加え、さらに１時間反応を行った。続いて、アクリロイルクロリド１８１ｇ（２．００モル）を１時間かけて滴下した。滴下中に反応熱により内温が上昇したので、６０℃以下となるように滴下量をコントロールした。全量滴下後反応温度を６０℃に保って、５時間反応を行った。その後、反応溶液を１０％ＮａＯＨ水溶液で中和した後、５％硫酸アンモニウム水溶液１５０ｇで洗浄した。トルエンを減圧蒸留して、多官能（メタ）アクリルモノマー（ＳｉＡ－００３）４４０ｇを得た。２５℃における粘度は３１０ｍＰａ・ｓであった。 [Production Example 2D: Production of SiA-002]
In a 1 liter four-neck flask equipped with a sufficiently dried stirring blade and a thermometer, 287 g (1.00 mol) of 1,3-Bis(3-chloropropyl)-1,1,3,3-tetramethyldisiloxane, After adding 0.30 g of BHT and 500 g of toluene and stirring until uniform, the temperature was raised to 60°C. Subsequently, 593 g (2.00 mol) of octamethylcyclotetrasiloxane was added dropwise over 1 hour. After dropping the entire amount, the reaction temperature was maintained at 60°C and the reaction was carried out for 6 hours. Thereafter, 740 g (2.00 mol) of octaethylene glycol was added to the reaction vessel, and the reaction was further carried out for 1 hour. Subsequently, 181 g (2.00 mol) of acryloyl chloride was added dropwise over 1 hour. Since the internal temperature rose due to reaction heat during the dropping, the dropping amount was controlled to be 60°C or less. After dropping the entire amount, the reaction temperature was maintained at 60°C and the reaction was carried out for 5 hours. Thereafter, the reaction solution was neutralized with a 10% NaOH aqueous solution, and then washed with 150 g of a 5% ammonium sulfate aqueous solution. Toluene was distilled under reduced pressure to obtain 440 g of polyfunctional (meth)acrylic monomer (SiA-003). The viscosity at 25°C was 310 mPa·s.
［製造例２Ｅ：ＳｉＡ－００３の製造］
　十分に乾燥させた撹拌羽根、及び温度計を備えた１リットル４ツ口フラスコ内に、ヘキサメチルシクロトリシロキサン６６７ｇ（３．００モル）、トルエン１００ｍＬ、テトラヒドロフラン２００ｍＬ、及びヘキサン１００ｍＬを添加し、均一となるまで撹拌した。その後、氷冷下でブチルリチウム（約１５％ヘキサン溶液）２ｍＬを１時間かけて滴下した。全量滴下後反応温度を室温に保って、２時間反応を行った。続いて、別の滴下漏斗に添加したアクリル酸３－（クロロジメチルシリル）プロピル２０７ｇ（１．００モル）を１時間かけて滴下した。全量滴下後反応温度を３０℃に保って、２４時間反応を行った。この際、ＨＰＬＣ分析で反応の進行を追跡して、反応の終点を確認した。その後、反応溶液を１０％ＮａＯＨ水溶液で中和した後、５％硫酸アンモニウム水溶液１５０ｇで洗浄した。溶媒を減圧蒸留して、多官能（メタ）アクリルモノマー（ＳｉＡ－００３）８１２ｇを得た。２５℃における粘度は２８０ｍＰａ・ｓであった。 [Production Example 2E: Production of SiA-003]
667 g (3.00 moles) of hexamethylcyclotrisiloxane, 100 mL of toluene, 200 mL of tetrahydrofuran, and 100 mL of hexane were added to a 1 liter 4-necked flask equipped with a sufficiently dried stirring blade and a thermometer, and the mixture was homogenized. Stir until . Thereafter, 2 mL of butyllithium (approximately 15% hexane solution) was added dropwise over 1 hour under ice cooling. After dropping the entire amount, the reaction temperature was kept at room temperature and the reaction was carried out for 2 hours. Subsequently, 207 g (1.00 mol) of 3-(chlorodimethylsilyl)propyl acrylate, which had been added to another dropping funnel, was added dropwise over 1 hour. After dropping the entire amount, the reaction temperature was maintained at 30°C and the reaction was carried out for 24 hours. At this time, the progress of the reaction was followed by HPLC analysis to confirm the end point of the reaction. Thereafter, the reaction solution was neutralized with a 10% NaOH aqueous solution, and then washed with 150 g of a 5% ammonium sulfate aqueous solution. The solvent was distilled under reduced pressure to obtain 812 g of polyfunctional (meth)acrylic monomer (SiA-003). The viscosity at 25°C was 280 mPa·s.
＜その他モノマー＞
　表４～表７に記載のその他モノマーの各々の構造は以下のとおりである。
ＬＡ　　　　　第一工業製薬株式会社製
９ＥＧ－Ａ　　第一工業製薬株式会社製 <Other monomers>
The structures of each of the other monomers listed in Tables 4 to 7 are as follows.
LA manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 9EG-A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
＜光重合開始剤＞
　表４～表７に記載の光重合開始剤としては、前述の光重合開始剤１（アシルフォスフィンオキサイド系化合物、Ｏｍｎｉｒａｄ　８１９：ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製「Ｏｍｎｉｒａｄ　８１９」）を使用した。 <Photopolymerization initiator>
As the photopolymerization initiator listed in Tables 4 to 7, the aforementioned photopolymerization initiator 1 (acylphosphine oxide compound, Omnirad 819: "Omnirad 819" manufactured by IGM Resins B.V.) was used.
　表４～７に示すように、実施例２０～４３において、変形性に優れ、かつ、形状回復性に優れた硬化物を得ることができた。
　一方、比較例４～８において得られた硬化物は変形性及び形状回復性の効果が実施例２０～４３と比較して劣っていた。
　さらに、実施例２０～４３において、離型性及び靱性の評価も良好であった。 As shown in Tables 4 to 7, in Examples 20 to 43, cured products with excellent deformability and shape recovery were obtained.
On the other hand, the cured products obtained in Comparative Examples 4 to 8 were inferior in deformability and shape recovery effects compared to Examples 20 to 43.
Furthermore, in Examples 20 to 43, the evaluation of mold releasability and toughness was also good.
　２０２２年３月２８日に出願された日本国特許出願２０２２－０５２２２８号及び２０２３年３月８日に出願された日本国特許出願２０２３－０３６０５１号の開示はその全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosures of Japanese Patent Application No. 2022-052228 filed on March 28, 2022 and Japanese Patent Application No. 2023-036051 filed on March 8, 2023 are incorporated herein by reference in their entirety. It will be done.
All documents, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference. Incorporated herein by reference.

Claims (20)

  1. 　（メタ）アクリルモノマー成分と、光重合開始剤と、を含む光硬化性組成物であって、
    　前記光硬化性組成物に対し波長４０５ｎｍの可視光を照射量１１ｍＪ／ｃｍ２にて照射して厚み５０μｍの硬化層Ａ１を形成し、前記硬化層Ａ１を厚み方向に積層させることにより、長さ４０ｍｍ、幅１０ｍｍ、厚み１．０ｍｍの矩形板形状の造形物Ａ１を形成し、前記造形物Ａ１に対し、波長３６５ｎｍの紫外線を照射量３Ｊ／ｃｍ２にて照射する条件の光造形により、長さ４０ｍｍ、幅１０ｍｍ、厚み１．０ｍｍの矩形板形状の試験片Ａ１を作製した場合に、
    　前記試験片Ａ１の２５℃における貯蔵弾性率が１０ＭＰａ以上であり、
    　前記試験片Ａ１の３７℃における貯蔵弾性率が４００ＭＰａ以下である、光硬化性組成物。     A photocurable composition comprising a (meth)acrylic monomer component and a photopolymerization initiator,
    A cured layer A1 having a thickness of 50 μm is formed by irradiating the photocurable composition with visible light having a wavelength of 405 nm at a dose of 11 mJ/cm 2 , and by laminating the cured layer A1 in the thickness direction, the length A rectangular plate-shaped object A1 with a width of 40 mm, a width of 10 mm, and a thickness of 1.0 mm is formed, and the object A1 is irradiated with ultraviolet light with a wavelength of 365 nm at a dose of 3 J/cm 2 to form a long object. When a rectangular plate-shaped test piece A1 with a length of 40 mm, a width of 10 mm, and a thickness of 1.0 mm was prepared,
    The storage modulus of the test piece A1 at 25°C is 10 MPa or more,
    A photocurable composition in which the storage modulus of the test piece A1 at 37° C. is 400 MPa or less.
  2. 　前記（メタ）アクリルモノマー成分が、
    　１つの（メタ）アクリロイルオキシ基と、芳香環と、を有するモノ（メタ）アクリルモノマー（Ｘ）と、
    　環構造又はウレタン結合の少なくともいずれか一方と、２つの（メタ）アクリロイルオキシ基と、を有し、シロキサン結合を有さないジ（メタ）アクリルモノマー（Ｙ）と、
    　シロキサン結合と、２つ以上の（メタ）アクリロイルオキシ基と、を有する多官能（メタ）アクリルモノマー（Ｚ）と、を含む、請求項１に記載の光硬化性組成物。     The (meth)acrylic monomer component is
    A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring,
    A di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and having no siloxane bond;
    The photocurable composition according to claim 1, comprising a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups.
  3. 　（メタ）アクリルモノマー成分と、光重合開始剤と、を含む光硬化性組成物であって、
    　前記（メタ）アクリルモノマー成分が、
    　１つの（メタ）アクリロイルオキシ基と、芳香環と、を有するモノ（メタ）アクリルモノマー（Ｘ）と、
    　環構造又はウレタン結合の少なくともいずれか一方と、２つの（メタ）アクリロイルオキシ基と、を有し、シロキサン結合を有さないジ（メタ）アクリルモノマー（Ｙ）と、
    　シロキサン結合と、２つ以上の（メタ）アクリロイルオキシ基と、を有する多官能（メタ）アクリルモノマー（Ｚ）と、を含む、光硬化性組成物。     A photocurable composition comprising a (meth)acrylic monomer component and a photopolymerization initiator,
    The (meth)acrylic monomer component is
    A mono(meth)acrylic monomer (X) having one (meth)acryloyloxy group and an aromatic ring,
    A di(meth)acrylic monomer (Y) having at least one of a ring structure or a urethane bond and two (meth)acryloyloxy groups and having no siloxane bond;
    A photocurable composition comprising a polyfunctional (meth)acrylic monomer (Z) having a siloxane bond and two or more (meth)acryloyloxy groups.
  4. 　前記ジ（メタ）アクリルモノマー（Ｙ）の分子量が、４００～５０００である、請求項２又は請求項３に記載の光硬化性組成物。 The photocurable composition according to claim 2 or 3, wherein the di(meth)acrylic monomer (Y) has a molecular weight of 400 to 5,000.
  5. 　前記多官能（メタ）アクリルモノマー（Ｚ）の分子量が、４００～５０００である、請求項２又は請求項３に記載の光硬化性組成物。 The photocurable composition according to claim 2 or 3, wherein the polyfunctional (meth)acrylic monomer (Z) has a molecular weight of 400 to 5,000.
  6. 　前記モノ（メタ）アクリルモノマー（Ｘ）の含有量が、前記（メタ）アクリルモノマー成分の全量に対し、３０質量％～９０質量％である、請求項２又は請求項３に記載の光硬化性組成物。 The photocurable material according to claim 2 or 3, wherein the content of the mono(meth)acrylic monomer (X) is 30% by mass to 90% by mass with respect to the total amount of the (meth)acrylic monomer component. Composition.
  7. 　前記ジ（メタ）アクリルモノマー（Ｙ）の含有量が、前記（メタ）アクリルモノマー成分の全量に対し、５質量％～５５質量％である、請求項２又は請求項３に記載の光硬化性組成物。 The photocurable material according to claim 2 or 3, wherein the content of the di(meth)acrylic monomer (Y) is 5% by mass to 55% by mass with respect to the total amount of the (meth)acrylic monomer component. Composition.
  8. 　前記多官能（メタ）アクリルモノマー（Ｚ）の含有量が、前記（メタ）アクリルモノマー成分の全量に対し、１質量％～６０質量％である、請求項２又は請求項３に記載の光硬化性組成物。 The photocuring according to claim 2 or 3, wherein the content of the polyfunctional (meth)acrylic monomer (Z) is 1% by mass to 60% by mass with respect to the total amount of the (meth)acrylic monomer component. sexual composition.
  9. 　組成物におけるシロキサン結合濃度が、０．１００ｍｍｏｌ／ｇ～３．０００ｍｍｏｌ／ｇである、請求項２又は請求項３に記載の光硬化性組成物。 The photocurable composition according to claim 2 or 3, wherein the siloxane bond concentration in the composition is 0.100 mmol/g to 3.000 mmol/g.
  10. 　前記（メタ）アクリルモノマー成分における芳香環濃度が、０．００１５ｍｏｌ／ｇ～０．００７０ｍｏｌ／ｇである、請求項２又は請求項３に記載の光硬化性組成物。 The photocurable composition according to claim 2 or 3, wherein the aromatic ring concentration in the (meth)acrylic monomer component is 0.0015 mol/g to 0.0070 mol/g.
  11. 　前記（メタ）アクリルモノマー成分が、２つの（メタ）アクリロイルオキシ基と、芳香環とを有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離が、２５Å以上８０Å以下あるジ（メタ）アクリルモノマー（Ａ）を含む、請求項１に記載の光硬化性組成物。 The (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the other (meth)acryloyloxy group. The photocurable composition according to claim 1, comprising a di(meth)acrylic monomer (A) having a distance of 25 Å or more and 80 Å or less from an oxygen atom forming an oxy group in an acryloyloxy group.
  12. 　以下の（ａ）及び（ｂ）のいずれかの条件を満たす、請求項１に記載の光硬化性組成物。
    　（ａ）前記（メタ）アクリルモノマー成分が、２つの（メタ）アクリロイルオキシ基と、芳香環とを有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離が、２５Å以上８０Å以下あるジ（メタ）アクリルモノマー（Ａ）を２種類以上含む。
    　（ｂ）前記（メタ）アクリルモノマー成分が、
    　２つの（メタ）アクリロイルオキシ基と、芳香環とを有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離が、２５Å以上８０Å以下あるジ（メタ）アクリルモノマー（Ａ）と、
    　２つの（メタ）アクリロイルオキシ基と、芳香環及びウレタン結合の少なくとも一方と、を有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離が、１０Å以上２５Å未満であるジ（メタ）アクリルモノマー（Ｂ－１）、
    　２つの（メタ）アクリロイルオキシ基と、芳香環及びウレタン結合の少なくとも一方と、を有し、一方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、他方の（メタ）アクリロイルオキシ基中のオキシ基を形成する酸素原子と、の間の距離が、８０Å超２００Å未満であるジ（メタ）アクリルモノマー（Ｂ－２）、及び
    　１つの（メタ）アクリロイルオキシ基と、芳香環及びヒドロキシ基の少なくとも一方と、を有するモノ（メタ）アクリルモノマー（Ｂ－３）からなる群から選択される１つ以上の（メタ）アクリルモノマー（Ｂ）と、を含む。     The photocurable composition according to claim 1, which satisfies either of the following conditions (a) and (b).
    (a) The (meth)acrylic monomer component has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group and the other Two or more types of di(meth)acrylic monomers (A) having a distance of 25 Å or more and 80 Å or less from the oxygen atom forming the oxy group in the (meth)acryloyloxy group are included.
    (b) the (meth)acrylic monomer component is
    It has two (meth)acryloyloxy groups and an aromatic ring, and the oxygen atom forming the oxy group in one (meth)acryloyloxy group forms the oxy group in the other (meth)acryloyloxy group. A di(meth)acrylic monomer (A) having a distance of 25 Å or more and 80 Å or less between the oxygen atom and
    having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, an oxygen atom forming an oxy group in one (meth)acryloyloxy group, and the other (meth)acryloyloxy A di(meth)acrylic monomer (B-1) in which the distance between the oxygen atom forming the oxy group in the group is 10 Å or more and less than 25 Å,
    having two (meth)acryloyloxy groups and at least one of an aromatic ring and a urethane bond, an oxygen atom forming an oxy group in one (meth)acryloyloxy group, and the other (meth)acryloyloxy A di(meth)acrylic monomer (B-2) in which the distance between the oxygen atom forming the oxy group in the group is more than 80 Å and less than 200 Å, and one (meth)acryloyloxy group and an aromatic ring and and one or more (meth)acrylic monomers (B) selected from the group consisting of mono(meth)acrylic monomers (B-3) having at least one hydroxy group.
  13. 　Ｅ型粘度計により２５℃及び５０ｒｐｍの条件で測定される粘度が、５ｍＰａ・ｓ～６０００ｍＰａ・ｓである、請求項１～請求項３のいずれか１項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 3, which has a viscosity of 5 mPa·s to 6000 mPa·s as measured by an E-type viscometer at 25° C. and 50 rpm.
  14. 　光造形用の光硬化性組成物である、請求項１～請求項３のいずれか１項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 3, which is a photocurable composition for stereolithography.
  15. 　光造形による鋳型の製造に用いられる光硬化性組成物である、請求項１～請求項３のいずれか１項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 3, which is a photocurable composition used for manufacturing a mold by stereolithography.
  16. 　請求項１～請求項３のいずれか１項に記載の光硬化性組成物の硬化物を含む、立体造形物。 A three-dimensional object comprising a cured product of the photocurable composition according to any one of claims 1 to 3.
  17. 　請求項１６に記載の立体造形物を含む、鋳型。 A mold comprising the three-dimensional structure according to claim 16.
  18. 　有床義歯の製造に用いられる、請求項１７に記載の鋳型。 The mold according to claim 17, which is used for manufacturing dentures.
  19. 　請求項１７に記載の鋳型内で硬化性組成物を重合させる工程を含む、硬化物の製造方法。 A method for producing a cured product, comprising a step of polymerizing a curable composition in the mold according to claim 17.
  20. 　光硬化性組成物を光造形により硬化させ、有床義歯の製造に用いられる鋳型を作製する工程と、
    　前記鋳型内で硬化性組成物を重合させ、有床義歯を製造する工程と、を含む、有床義歯の製造方法。     a step of curing the photocurable composition by stereolithography to produce a mold used for manufacturing a denture;
    A method for producing a denture with a denture, comprising the step of polymerizing a curable composition in the mold to produce a denture with a denture.
PCT/JP2023/011620 2022-03-28 2023-03-23 Photosetting composition, three-dimensionally shaped article, mold, method for manufacturing cured product, and method for manufacturing plate denture WO2023190071A1 (en)

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JP2018502624A (en) * 2014-12-09 2018-02-01 ヘレーウス クルツァー ゲゼルシャフト ミット ベシュレンクテル ハフツングＨｅｒａｅｕｓ Ｋｕｌｚｅｒ ＧｍｂＨ Method for making a dental prosthesis using a template
JP2016172796A (en) * 2015-03-16 2016-09-29 東洋インキＳｃホールディングス株式会社 Active energy ray-polymerizable resin composition for stereolithography, and three-dimensional molded object
WO2018105463A1 (en) * 2016-12-05 2018-06-14 Dic株式会社 Photocurable resin composition for optical stereolithography
JP2020525191A (en) * 2017-07-03 2020-08-27 シロナ・デンタル・システムズ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Method for producing artificial gingiva
JP2019181932A (en) * 2018-04-16 2019-10-24 キヤノン株式会社 Curable resin composition for solid molding
JP2020147623A (en) * 2019-03-11 2020-09-17 Dic株式会社 Cured product, three-dimensional shaped product and method for producing cured product

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